Substrate processing method and substrate processing device

Abstract

A rinse liquid containing water is supplied to the upper surface of the substrate. The rinse liquid on the upper surface of the substrate is replaced by the first liquid. The first liquid on the upper surface of the substrate is replaced by the second liquid. The second liquid on the upper surface of the substrate is removed, thereby drying the substrate. The solubility of the second liquid in water is less than the solubility of the first liquid in water. The surface tension of the second liquid is lower than the surface tension of the first liquid. The specific gravity of the second liquid is greater than the specific gravity of the first liquid. The boiling point of the second liquid is above room temperature, and the value obtained by subtracting room temperature from the boiling point of the second liquid is below room temperature.

Description

Technical Field

[0001] This application claims priority based on Japanese Patent Application No. 2019-079465 filed on April 18, 2019, the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to a substrate processing method and a substrate processing device for drying a substrate. The substrate includes, for example, a semiconductor wafer, a liquid crystal display device, an organic EL (electroluminescence) display device, a FPD (Flat Panel Display) substrate, an optical disk substrate, a magnetic disk substrate, an optical disk substrate, a photomask substrate, a ceramic substrate, a solar cell substrate, and the like. Background Art

[0003] In the manufacturing process of semiconductor devices, FPDs, etc., substrates such as semiconductor wafers and glass substrates for FPDs are subjected to treatments as required. Such treatments include supplying treatment liquids such as chemical liquids and rinse liquids to the substrates. After the treatment liquids are supplied, the treatment liquids are removed from the substrates to dry the substrates. Patent Documents 1 and 2 disclose the following: chemical liquids, pure water, IPA (isopropyl alcohol), and HFE (hydrofluoroether) are supplied to the substrates in this order, and then the substrates are dried.

[0004] In paragraph 0021 of Patent Document 1, it is described that "As the "HFE liquid", for example, HFE of the Novec (registered trademark) series manufactured by Sumitomo 3M Limited can be used. Specifically, as HFE, for example, Novec 7100 / 7100DL (chemical formula: C4F9OCH3), Novec 7200 (chemical formula: C4F9OC2H5), Novec 7300 (chemical formula: C6F 13 OCH3) and the like. ". In paragraph 0059 of Patent Document 1, it is described that "HFE71IPA (hydrofluoroether azeotropic mixture) of the Novec (registered trademark) series manufactured by Sumitomo 3M Limited, for example, can also be used." Patent Document 2 does not particularly specify the type of HFE.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2010-50143

[0008] Patent Document 2: Japanese Patent Application Publication No. 2008-128567 Summary of the invention

[0009] Problems to be solved by the invention

[0010] Removing the liquid attached to the substrate immediately before drying in a short time is extremely important in suppressing pattern collapse. This is because if the liquid is removed from the substrate in a short time, the time for the collapse force that causes the pattern to collapse can be shortened. The boiling point of Novec 7100 described in Patent Document 1 is 61°C, which is relatively low. However, according to the research of the inventors of this application, even if a liquid with such a boiling point is used, the collapse of the pattern cannot be fully suppressed depending on the strength of the pattern.

[0011] Therefore, one of the objects of the present invention is to provide a substrate processing method and a substrate processing apparatus capable of drying a substrate while suppressing the collapse of a pattern.

[0012] Means for solving problems

[0013] One embodiment of the present invention provides a substrate processing method, which is a method for drying the substrate while keeping the substrate horizontal, the method comprising the following steps: a rinsing liquid supplying step of supplying a rinsing liquid containing water to the upper surface of the substrate; a first replacement step of supplying a first liquid to the upper surface of the substrate, thereby replacing the rinsing liquid on the upper surface of the substrate with the first liquid; a second replacement step of supplying a second liquid to the upper surface of the substrate, thereby replacing the first liquid on the upper surface of the substrate with the second liquid; and a drying step of removing the second liquid on the upper surface of the substrate, thereby drying the substrate, wherein the solubility of the second liquid in water is lower than the solubility of the first liquid in water, the surface tension of the second liquid is lower than the surface tension of the first liquid, the specific gravity of the second liquid is greater than the specific gravity of the first liquid, the boiling point of the second liquid (the boiling point at 1 atmosphere, the same below) is above room temperature, and the value obtained by subtracting the room temperature from the boiling point of the second liquid is below the room temperature.

[0014] According to this method, a rinse liquid containing water is supplied to the upper surface of a substrate held horizontally. Thereafter, a first liquid is supplied to the upper surface of the substrate held horizontally. Thus, the rinse liquid on the upper surface of the substrate is replaced by the first liquid. Thereafter, a second liquid is supplied to the upper surface of the substrate held horizontally. Thus, the first liquid on the upper surface of the substrate is replaced by the second liquid. Therefore, the rinse liquid is replaced by the second liquid in stages. Thereafter, the second liquid is removed from the upper surface of the substrate to dry the substrate.

[0015] The rinsing liquid on the substrate is not directly replaced by the second liquid, but is replaced by the second liquid after being replaced by the first liquid. The solubility of the second liquid in water is less than the solubility of the first liquid in water. That is, compared with the first liquid, the second liquid has a low affinity for water. If the second liquid is supplied to the upper surface of the substrate that keeps the rinsing liquid, then the rinsing liquid sometimes remains in the upper surface of the substrate. If the residual amount of the rinsing liquid that contains water that the surface tension is high is many, then when the substrate is dried, the collapse of the pattern occurs easily. If the first liquid with a relatively high affinity for water is replaced with the rinsing liquid, the rinsing liquid that remains on the substrate before being dried can be reduced.

[0016] In addition, the specific gravity of the second liquid is greater than that of the first liquid. Therefore, at the interface between the first liquid and the second liquid, the second liquid moves toward the upper surface side of the substrate due to gravity, and the first liquid moves onto the second liquid. That is, the second liquid enters between the first liquid and the substrate due to the difference in specific gravity. In addition, since the surface tension of the second liquid is low and the specific gravity of the second liquid is large, the second liquid enters between the patterns, and the first liquid located between the patterns is replaced by the second liquid. Since the second liquid with such low surface tension enters between the patterns, when the substrate is dried, even if the surface of the second liquid is formed between the patterns, the collapse of the patterns can be reduced.

[0017] The boiling point of the second liquid is above room temperature. Therefore, when using the second liquid under the environment of room temperature, the second liquid can be cooled down without being maintained as a liquid. In addition, the value obtained by deducting room temperature from the boiling point of the second liquid is below room temperature. That is, the boiling point of the second liquid is a value in the range of 2 times the value of room temperature to room temperature, which is relatively low relative to room temperature. If the boiling point of the second liquid is low, the speed at which the second liquid disappears from the substrate rises during the drying process of the substrate, so the time when the collapse force that makes the pattern collapse is applied to the pattern can be shortened. Thus, the collapse of the pattern can be reduced, and the quality of the substrate after drying can be improved.

[0018] The rinse liquid may be water such as pure water, or an aqueous solution containing water as a main component (for example, an aqueous solution having a volume percentage concentration of water of 50 vol % or more).

[0019] In the aforementioned embodiment, at least one of the following features may be added to the aforementioned substrate processing method.

[0020] The above-mentioned rinsing liquid supplying process includes the process of supplying the above-mentioned rinsing liquid to the upper surface of the above-mentioned substrate while rotating the above-mentioned substrate at a rinsing liquid supplying speed, and the above-mentioned second replacement process includes the process of supplying the above-mentioned second liquid to the upper surface of the above-mentioned substrate while rotating the above-mentioned substrate at a second replacement speed smaller than the above-mentioned rinsing liquid supplying speed.

[0021] According to this method, while the substrate is rotated at a low speed, the first liquid on the upper surface of the substrate is replaced by the second liquid. If the supply of the second liquid is started, the upper surface of the substrate is covered by a roughly circular liquid film of the second liquid (also referred to as the "second liquid film") and a ring-shaped liquid film of the first liquid (also referred to as the "first liquid film") surrounding the second liquid film. Thereafter, the outer periphery of the second liquid film slowly expands toward the outer periphery of the upper surface of the substrate while maintaining a roughly circular state. In the case where the properties of the first liquid and the second liquid are greatly different, if the substrate is rotated at a high speed, there is the following concern: the outer periphery of the second liquid film will not expand while maintaining a roughly circular state, and the first liquid is not effectively replaced. If the substrate is rotated at a low speed, such a phenomenon can be prevented before it occurs.

[0022] The second replacement process includes the following partial replacement process: only a portion of the first liquid on the upper surface of the substrate is replaced by the second liquid, thereby maintaining the liquid film of the second liquid and the liquid film of the first liquid surrounding the liquid film of the second liquid on the upper surface of the substrate.

[0023] According to this method, only a portion of the first liquid on the upper surface of the substrate is replaced by the second liquid. As a result, the annular first liquid film remains at least on the outer peripheral portion of the upper surface of the substrate, and the second liquid is retained on the inner side of the first liquid film. Since the surface tension of the second liquid is low, if the entire first liquid on the upper surface of the substrate is replaced by the second liquid, a thin second liquid film is formed on the upper surface of the substrate. In addition, since the boiling point of the second liquid is low, if the supply of new second liquid is stopped, the second liquid on the substrate may evaporate rapidly, and a portion of the upper surface of the substrate may be exposed from the second liquid film in a short time.

[0024] In contrast, since the surface tension of the first liquid is higher than that of the second liquid, the thickness of the first liquid film remaining on the outer peripheral portion of the upper surface of the substrate is greater than the thickness of the second liquid film. The second liquid supplied to the upper surface of the substrate is retained inside the annular first liquid film. Therefore, compared with the case where all the first liquid on the upper surface of the substrate is replaced by the second liquid, a thicker second liquid film is formed inside the first liquid film. Thus, it is possible to prevent a portion of the upper surface of the substrate from being exposed from the second liquid film in a short time.

[0025] The aforementioned substrate processing method also includes a liquid discharge process of discharging the liquid film of the aforementioned second liquid from the upper surface of the aforementioned substrate before the aforementioned drying process, and the aforementioned liquid discharge process includes the following processes: a hole forming process, forming an exposure hole that only exposes a portion of the upper surface of the aforementioned substrate on the liquid film of the aforementioned second liquid; and a hole enlarging process, expanding the outer edge of the aforementioned exposure hole to the periphery of the upper surface of the aforementioned substrate.

[0026] According to this method, in a state where the second liquid film is maintained on the upper surface of the substrate, an exposure hole that exposes only a portion of the upper surface of the substrate is formed on the second liquid film. Thereafter, the outer edge of the exposure hole is extended to the periphery of the upper surface of the substrate. Thus, droplets of a size that can be visually observed disappear from the upper surface of the substrate, and the entire area of ​​the upper surface of the substrate is exposed. That is, while controlling the shape of the second liquid film, the second liquid film is discharged from the upper surface of the substrate. Therefore, compared with the case where the second liquid film is discharged in a disorderly manner, the quality of the substrate after drying can be stabilized.

[0027] The above-mentioned rinsing liquid supplying process includes the process of supplying the above-mentioned rinsing liquid to the upper surface of the above-mentioned substrate while rotating the above-mentioned substrate at a rinsing liquid supplying speed, and the above-mentioned hole enlarging process includes the process of extending the outer edge of the above-mentioned exposed hole to the periphery of the upper surface of the above-mentioned substrate while rotating the above-mentioned substrate at a liquid discharge speed lower than the above-mentioned rinsing liquid supplying speed.

[0028] According to this method, while the substrate is rotated at a low speed, the inner diameter and outer diameter of the annular second liquid film having the exposure hole formed therein and the inner diameter of the annular first liquid film surrounding the second liquid film are increased. In the case where the properties of the first liquid and the second liquid are greatly different, if the substrate is rotated at a high speed, there is a concern that the outer periphery of the second liquid film will not extend to the outer periphery of the upper surface of the substrate while maintaining a substantially circular state, and the first liquid will remain on the outer periphery of the upper surface of the substrate. If the substrate is rotated at a low speed, such a phenomenon can be prevented in advance.

[0029] The hole enlarging step includes a step of extending the outer edge of the exposure hole to the outer periphery of the upper surface of the substrate while rotating the substrate at a rotation speed greater than 0 and not more than 50 rpm.

[0030] According to this method, while the substrate is rotated at a rotation speed greater than 0 and less than 50 rpm, the inner diameter and outer diameter of the annular second liquid film formed with the exposure hole and the inner diameter of the annular first liquid film surrounding the second liquid film are increased. Since the centrifugal force applied to the second liquid is small, the inner and outer peripheries of the second liquid film are slowly expanded. Thus, the outer periphery of the second liquid film can be expanded to the outer periphery of the upper surface of the substrate while being kept in a substantially circular state, and the amount of the first liquid remaining in the outer periphery of the upper surface of the substrate can be reduced to zero or near zero.

[0031] The hole forming step includes a heating fluid supplying step of ejecting a heating fluid having a temperature higher than the room temperature toward only a portion of the lower surface of the substrate.

[0032] According to this method, a heating fluid having a higher temperature than room temperature is ejected only toward a portion of the lower surface of the substrate. After the heating fluid collides with the lower surface of the substrate, it spreads along the lower surface of the substrate. The substrate is heated by the heating fluid. The second liquid is heated by the substrate. The evaporation amount of the second liquid per unit time is the largest on the opposite side of the position where the heating fluid collides with the lower surface of the substrate. Therefore, the position where the exposure hole is formed can be controlled.

[0033] The heating fluid can be a liquid or gas with a higher temperature than room temperature, or a mixed fluid containing a liquid and a gas with a higher temperature than room temperature. The temperature of the heating fluid can be a temperature higher than the boiling point of the second liquid. When the temperature of the heating fluid is higher than the boiling point of the second liquid, the second liquid is vaporized on the opposite side of the position where the heating fluid collides with the lower surface of the substrate, and a large number of small bubbles are between the second liquid and the upper surface of the substrate. Thus, the second liquid leaves the upper surface of the substrate. In this case, if the thickness of the vapor layer containing the vapor of the second liquid is greater than the height of the pattern, all of the second liquid disappears from between the patterns. Therefore, the collapse of the pattern can be prevented, and the second liquid film is discharged from the substrate.

[0034] The hole forming step includes a uniform heating step of causing a heater disposed below the substrate so as to overlap the substrate in a plan view to generate heat.

[0035] According to this method, a heater disposed below the substrate in a manner overlapping with the substrate when viewed from above is heated. The substrate is heated by the heater. The second liquid is heated by the substrate. Thus, an exposure hole penetrating the second liquid film can be formed. In addition, compared with a case where a heating fluid having a temperature higher than room temperature is ejected only toward a portion of the lower surface of the substrate, the heater can directly heat a wide range. Thus, the substrate and the second liquid film can be uniformly heated.

[0036] The temperature of the heater can be above the boiling point of the second liquid. If the temperature of the upper surface of the substrate (the surface including the pattern when a pattern is formed) is above the boiling point of the second liquid, the second liquid vaporizes at the interface between the second liquid film and the substrate, and a large number of small bubbles are between the second liquid and the upper surface of the substrate. If the second liquid vaporizes at all positions at the interface between the second liquid film and the substrate, a vapor layer containing the vapor of the second liquid is formed between the second liquid film and the substrate. As a result, the second liquid leaves the upper surface of the substrate, and the second liquid film floats out from the upper surface of the substrate. At this time, the frictional resistance of the second liquid film acting on the substrate is so small that it can be regarded as zero. Therefore, the second liquid film can be discharged from the upper surface of the substrate with a small force.

[0037] The hole forming process includes the following scanning process: rotating the substrate around a vertical rotation axis passing through the central portion of the upper surface of the substrate, and, while spraying the second liquid toward the upper surface of the substrate, moving the position where the second liquid collides with the upper surface of the substrate from the central portion of the upper surface of the substrate to the peripheral side of the upper surface of the substrate.

[0038] According to this method, the second liquid nozzle is made to eject the second liquid while the substrate is rotated. In addition, the position where the second liquid ejected from the second liquid nozzle collides with the upper surface of the substrate is moved from the central part of the upper surface of the substrate to the peripheral side of the upper surface of the substrate. After the second liquid nozzle is moved, the supply of new second liquid to the central part of the upper surface of the substrate is stopped. In addition, the second liquid evaporates on the central part of the upper surface of the substrate and moves outward from the central part of the upper surface of the substrate due to centrifugal force. Therefore, only by moving the second liquid nozzle outward, an exposure hole can be formed in the central part of the upper surface of the substrate.

[0039] The aforementioned hole forming process may include a gas supply process of spraying gas toward the liquid film of the aforementioned second liquid on the upper surface of the aforementioned substrate. The temperature of the gas may be room temperature or higher than room temperature. The aforementioned hole forming process may include a heating process of causing a heater arranged above the aforementioned substrate to generate heat. The aforementioned gas supply process may be performed in parallel with the aforementioned heating fluid supply process, uniform heating process, or scanning process. The aforementioned heating process may be performed in parallel with the aforementioned heating fluid supply process, uniform heating process, scanning process, or gas supply process. The aforementioned heater may be a heating plate or a lamp, or may be a heater other than these. The aforementioned lamp may be an infrared lamp that emits infrared rays (for example, near-infrared rays), or an LED lamp that includes a light-emitting diode, or may be a lamp other than these.

[0040] If the gas is blown onto the second liquid film, the second liquid contained in the second liquid film is pushed outward due to the pressure of the gas. In addition, the evaporation of the second liquid is promoted by the supply of gas. In particular, when the temperature of the gas is higher than room temperature, the evaporation amount of the second liquid per unit time increases. As a result, the thickness of the second liquid film is reduced, and an exposure hole is formed on the second liquid film. In addition, the force that moves the second liquid outward is applied to the second liquid on the substrate due to the gas flowing outward along the surface of the second liquid film, and the second liquid flows outward along the upper surface of the substrate. As a result, the outer edge of the exposure hole can be expanded in the direction of the outer periphery of the upper surface of the substrate.

[0041] When the drying step is a step of removing the second liquid on the upper surface of the substrate by rotating the substrate at a high rotation speed higher than the supply speed of the rinse liquid, the hole forming step may include a rotation hole forming step of stopping the supply of the new second liquid to the upper surface of the substrate and rotating the substrate at a liquid discharge speed lower than the high rotation speed around a vertical rotation axis passing through the center of the upper surface of the substrate. The rotation hole forming step may be performed in parallel with the heating fluid supply step, the uniform heating step, the scanning step, the gas supply step, or the heat generation step, or may be performed separately.

[0042] Because the boiling point of the second liquid is low, therefore, if the supply of new second liquid to the upper surface of the substrate is stopped, the second liquid evaporates, and the thickness of the second liquid film slowly decreases. In addition, if the substrate is rotated, centrifugal force is applied to the second liquid, and the second liquid flows outward along the upper surface of the substrate. Although the second liquid flows from the inner side of the upper surface of the substrate to the position outside the central part of the upper surface of the substrate, the second liquid will not flow to the central part of the upper surface of the substrate. Therefore, if the supply of the second liquid is stopped for a while, an exposure hole that penetrates the second liquid film is formed. Thus, the exposure hole can be formed only by rotating the substrate.

[0043] The substrate processing method includes a condensation prevention step of maintaining the temperature of the upper surface of the substrate at a value higher than the dew point temperature of the second liquid in parallel with the liquid discharge step.

[0044] According to this method, when the exposure hole is formed on the second liquid film and the outer edge of the exposure hole is extended to the outer peripheral side of the upper surface of the substrate, the temperature of the upper surface of the substrate is maintained at a value higher than the dew point temperature of the second liquid. After the exposure hole is formed, at least a portion of the upper surface of the substrate is exposed, and the vapor of the second liquid floats near the upper surface of the substrate. Therefore, by maintaining the temperature of the upper surface of the substrate at a value higher than the dew point temperature of the second liquid, it is possible to prevent the generation of droplets of the second liquid at the exposed portion of the upper surface of the substrate that has been exposed from the second liquid film. As a result, it is possible to reduce the collapse of the pattern at the exposed portion and the generation of particles.

[0045] The anti-condensation process may include at least one of the following processes: a fluid supply process, in which an anti-condensation fluid having a higher temperature than the dew point temperature is ejected toward at least one of the upper surface and the lower surface of the substrate; and a heating process, in which a heater disposed above or below the substrate is heated. When the dew point temperature of the second liquid is lower than room temperature, the anti-condensation fluid may be a liquid or gas at room temperature, or a mixed fluid at room temperature containing a liquid and a gas. The anti-condensation fluid may be the aforementioned heating fluid, or the aforementioned gas ejected toward the aforementioned second liquid film on the upper surface of the substrate in the aforementioned gas supply process. The aforementioned heater may be a heating plate or a lamp, or may be a heater other than these. The aforementioned lamp may be an infrared lamp emitting infrared rays (for example, near-infrared rays), or an LED lamp containing a light-emitting diode, or may be a lamp other than these.

[0046] Another embodiment of the present invention provides a substrate processing device, which comprises: a substrate holding unit, the substrate holding unit holds the substrate horizontally; a rinsing liquid supply unit, the rinsing liquid supply unit supplies a rinsing liquid containing water to the upper surface of the substrate held by the substrate holding unit; a first replacement unit, the first replacement unit supplies a first liquid to the upper surface of the substrate held by the substrate holding unit, thereby replacing the rinsing liquid on the upper surface of the substrate with the first liquid; a second replacement unit, the second replacement unit supplies a second liquid to the upper surface of the substrate held by the substrate holding unit 2 liquid, thereby replacing the first liquid on the upper surface of the substrate with the second liquid; and a drying unit, the drying unit removes the second liquid on the upper surface of the substrate held by the substrate holding unit, thereby drying the substrate, the solubility of the second liquid in water is lower than the solubility of the first liquid in water, the surface tension of the second liquid is lower than the surface tension of the first liquid, the specific gravity of the second liquid is greater than the specific gravity of the first liquid, the boiling point of the second liquid is above room temperature, and the value obtained by subtracting the room temperature from the boiling point of the second liquid is below the room temperature. According to this configuration, the same effect as the above effect can be exerted.

[0047] The aforementioned rinsing liquid supply unit may include a rinsing liquid nozzle for ejecting the aforementioned rinsing liquid. The aforementioned first replacement unit may include a first liquid nozzle for ejecting the aforementioned first liquid. The aforementioned second replacement unit may include a second liquid nozzle for ejecting the aforementioned second liquid. The aforementioned first liquid nozzle may be the aforementioned rinsing liquid nozzle, or may be a nozzle different from the aforementioned rinsing liquid nozzle. The aforementioned second liquid nozzle may be the aforementioned rinsing liquid nozzle or the first liquid nozzle, or may be a nozzle different from the aforementioned rinsing liquid nozzle and the first liquid nozzle. The aforementioned drying unit may include a rotary motor for rotating the aforementioned substrate around a vertical rotation axis passing through the center of the upper surface of the aforementioned substrate.

[0048] The foregoing and other objects, features, and effects of the present invention will become more apparent from the following description of the embodiments with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] [ Figure 1A ] is a schematic diagram of a substrate processing apparatus according to a first embodiment of the present invention as viewed from above.

[0050] [ Figure 1B ] is a schematic diagram of a substrate processing device viewed from the side.

[0051] [ Figure 2 ] is a schematic diagram showing the interior of a processing unit of a substrate processing apparatus when viewed horizontally.

[0052] [ Figure 3 ] is a block diagram showing the hardware of the control device.

[0053] [ Figure 4 ] is a process diagram for illustrating an example (first embodiment) of substrate processing performed by a substrate processing apparatus.

[0054] [ Figure 5A ] is a schematic diagram showing the state of the substrate when performing the first embodiment.

[0055] [ Figure 5B ] is a schematic diagram showing the state of the substrate when performing the first embodiment.

[0056] [ Figure 5C ] is a schematic diagram showing the state of the substrate when performing the first embodiment.

[0057] [ Figure 6 ] is a process diagram for illustrating another example (second embodiment) of substrate processing performed by a substrate processing apparatus.

[0058] [ Fig. 7A ] is a schematic diagram showing the state of the substrate when the second embodiment is performed.

[0059] [ Figure 7B ] is a schematic diagram showing the state of the substrate when the second embodiment is performed.

[0060] [ Figure 7C ] is a schematic diagram showing the state of the substrate when the second embodiment is performed.

[0061] [ Fig.7D ] is a schematic diagram showing the state of the substrate when the second embodiment is performed.

[0062] [ Fig. 7E ] is a schematic diagram showing the state of the substrate when the second embodiment is performed.

[0063] [ Figure 7F ] is a schematic diagram showing the state of the substrate when the second embodiment is performed.

[0064] [ Figure 8 ] is a process diagram for illustrating another example (third embodiment) of substrate processing performed by a substrate processing apparatus.

[0065] [ Fig.9A ] is a schematic diagram showing the state of the substrate when performing the third embodiment.

[0066] [ Fig. 9B ] is a schematic diagram showing the state of the substrate when performing the third embodiment.

[0067] [ Fig. 9C ] is a schematic diagram showing the state of the substrate when performing the third embodiment.

[0068] [ Fig.10 ] is a process diagram for illustrating another example (fourth embodiment) of substrate processing performed by a substrate processing apparatus.

[0069] [ Fig.11A ] is a schematic diagram showing the state of the substrate when performing the fourth embodiment.

[0070] [ Fig. 11B ] is a schematic diagram showing the state of the substrate when performing the fourth embodiment.

[0071] [ Fig. 11C ] is a schematic diagram showing the state of the substrate when performing the fourth embodiment.

[0072] [ Fig. 12A ] is a schematic diagram of a horizontal view of a spin chuck, a blocking member, and a heating plate according to a second embodiment of the present invention.

[0073] [ Fig. 12B ] is a schematic diagram of a spin chuck and a heating plate according to a second embodiment of the present invention as viewed from above.

[0074] [ Fig.13 ] is a process diagram for illustrating another example (the fifth embodiment) of substrate processing performed by a substrate processing apparatus.

[0075] [ Fig.14A ] is a schematic diagram showing the state of the substrate when performing the fifth embodiment.

[0076] [ Fig. 14B ] is a schematic diagram showing the state of the substrate when performing the fifth embodiment.

[0077] [ Fig. 14C] is a schematic diagram showing the state of the substrate when performing the fifth embodiment. DETAILED DESCRIPTION

[0078] Figure 1A It is a schematic diagram of the substrate processing apparatus 1 according to the first embodiment of the present invention as viewed from above. Figure 1B It is a schematic diagram of the substrate processing apparatus 1 viewed from the side.

[0079] like Figure 1A As shown, the substrate processing apparatus 1 is a single-wafer apparatus that processes disc-shaped substrates W such as semiconductor wafers one by one. The substrate processing apparatus 1 comprises: a loading port LP for holding a carrier CA for accommodating the substrates W; a plurality of processing units 2 for processing the substrates W removed from the carrier CA on the loading port LP using a processing fluid such as a processing liquid or a processing gas; a transport robot for transporting the substrates W between the carrier CA on the loading port LP and the processing unit 2; and a control device 3 for controlling the substrate processing apparatus 1.

[0080] The transport robot includes an indexer robot IR that carries substrates W in and out of a carrier CA on a load port LP, and a central robot CR that carries substrates W in and out of a plurality of processing units 2. The indexer robot IR carries substrates W between the load port LP and the central robot CR, and the central robot CR carries substrates W between the indexer robot IR and the processing units 2. The central robot CR includes a hand H1 that supports the substrate W, and the indexer robot IR includes a hand H2 that supports the substrate W.

[0081] The plurality of processing units 2 are formed with a plurality of towers TW arranged around the central robot CR in a plan view. Figure 1A An example is shown in which four towers TW are formed. The central robot CR can reach any tower TW. Figure 1B As shown, each tower TW includes a plurality of (eg, three) processing units 2 stacked one above the other.

[0082] Figure 2 It is a schematic diagram showing the interior of a processing unit 2 included in a substrate processing apparatus 1 when viewed horizontally.

[0083] The processing unit 2 is a wet processing unit that supplies a processing liquid to the substrate W. The processing unit 2 includes: a box-shaped chamber 4 having an internal space; a spin chuck 10 that holds a substrate W horizontally in the chamber 4 and rotates the substrate W around a vertical rotation axis A1 passing through the center of the substrate W; and a cylindrical processing cup 21 that surrounds the spin chuck 10 around the rotation axis A1.

[0084] The chamber 4 includes a box-shaped partition wall 5 provided with a loading and unloading port 5b for the substrate W to pass through, and a shutter 7 for opening and closing the loading and unloading port 5b. The FFU6 (fan filter unit) is arranged above the air supply port 5a arranged on the upper part of the partition wall 5. The FFU6 always supplies clean air (air filtered by a filter) into the chamber 4 from the air supply port 5a. The gas in the chamber 4 is discharged from the chamber 4 through the exhaust pipe 8 connected to the bottom of the processing cup 21. As a result, a downward flow of clean air is always formed in the chamber 4. The flow rate of the exhaust gas discharged to the exhaust pipe 8 changes according to the opening of the exhaust valve 9 arranged in the exhaust pipe 8.

[0085] The spin chuck 10 includes: a disk-shaped spin base 12 held in a horizontal posture; a plurality of chuck pins 11 above the spin base 12 holding the substrate W in a horizontal posture; a rotation shaft 13 extending downward from the center of the spin base 12; and a rotation motor 14 that rotates the spin base 12 and the plurality of chuck pins 11 by rotating the rotation shaft 13. The spin chuck 10 is not limited to a clamping chuck in which the plurality of chuck pins 11 are in contact with the outer peripheral surface of the substrate W, but may be a vacuum chuck in which the back side (lower surface) of the substrate W, which is a non-device forming surface, is adsorbed to the upper surface 12u of the spin base 12, thereby holding the substrate W horizontally.

[0086] The processing cup 21 includes: a plurality of shields 24 for blocking processing liquid discharged from the substrate W to the outside; a plurality of cups 23 for receiving the processing liquid guided downward by the plurality of shields 24; and a cylindrical outer wall member 22 surrounding the plurality of shields 24 and the plurality of cups 23. Figure 2 An example is shown in which four protective covers 24 and three cups 23 are provided, and the outermost cup 23 is integrated with the third protective cover 24 from the top.

[0087] The protective cover 24 includes: a cylindrical portion 25 surrounding the rotating chuck 10; and an annular top plate portion 26 extending obliquely upward from the upper end of the cylindrical portion 25 toward the rotation axis A1. A plurality of top plate portions 26 overlap up and down, and a plurality of cylindrical portions 25 are arranged in a concentric circle shape. When viewed from above, the annular upper end of the top plate portion 26 corresponds to the upper end 24u of the protective cover 24 surrounding the substrate W and the rotating base 12. A plurality of cups 23 are each arranged below the plurality of cylindrical portions 25. The cups 23 form an annular liquid receiving tank for receiving the processing liquid guided downward by the protective cover 24.

[0088] The processing unit 2 includes a protective cover lifting unit 27 for lifting each of the plurality of protective covers 24. The protective cover lifting unit 27 positions the protective cover 24 at any position from an upper position to a lower position. Figure 2The figure shows a state where two protective covers 24 are arranged at an upper position and the remaining two protective covers 24 are arranged at a lower position. The upper position is when the upper end 24u of the protective cover 24 is arranged above the holding position (the holding position is the position where the substrate W held by the spin chuck 10 is arranged). The lower position is when the upper end 24u of the protective cover 24 is arranged below the holding position.

[0089] When supplying the processing liquid to the rotating substrate W, at least one protective cover 24 is arranged at the upper position. In this state, when the processing liquid is supplied to the substrate W, the processing liquid is thrown off the substrate W to the outside. The thrown processing liquid collides with the inner surface of the protective cover 24 horizontally facing the substrate W, and is guided to the cup 23 corresponding to the protective cover 24. Thus, the processing liquid discharged from the substrate W is collected in the cup 23.

[0090] The processing unit 2 includes a plurality of nozzles for ejecting a processing liquid toward a substrate W held by a spin chuck 10. The plurality of nozzles include: a chemical liquid nozzle 31 for ejecting a chemical liquid toward an upper surface of the substrate W; a rinse liquid nozzle 35 for ejecting a rinse liquid toward an upper surface of the substrate W; a first liquid nozzle 39 for ejecting a first liquid toward an upper surface of the substrate W; and a second liquid nozzle 43 for ejecting a second liquid toward an upper surface of the substrate W.

[0091] The chemical liquid nozzle 31 may be a scanning nozzle that can move horizontally in the chamber 4, or may be a fixed nozzle that is fixed to the partition wall 5 of the chamber 4. The same is true for the rinse liquid nozzle 35, the first liquid nozzle 39, and the second liquid nozzle 43. Figure 2 In the example shown, the chemical liquid nozzle 31 , the rinse liquid nozzle 35 , the first liquid nozzle 39 , and the second liquid nozzle 43 are scanning nozzles, and four nozzle moving units corresponding to the four nozzles are provided.

[0092] The chemical liquid nozzle 31 is connected to a chemical liquid piping 32 that guides the chemical liquid to the chemical liquid nozzle 31. When a chemical liquid valve 33 installed on the chemical liquid piping 32 is opened, the chemical liquid is continuously ejected downward from the ejection port of the chemical liquid nozzle 31. The chemical liquid ejected from the chemical liquid nozzle 31 may be a liquid containing at least one of sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid, acetic acid, ammonia water, aqueous hydrogen peroxide solution, an organic acid (e.g., citric acid, oxalic acid, etc.), an organic base (e.g., TMAH: tetramethylammonium hydroxide, etc.), a surfactant, and an anticorrosive agent, or may be a liquid other than these.

[0093] Although not shown, the liquid medicine valve 33 includes: a valve body, which is provided with an annular valve seat for liquid medicine to pass through; a valve core, which is movable relative to the valve seat; and an actuator, which moves the valve core between a closed position (the valve core is in contact with the valve seat) and an open position (the valve core is away from the valve seat). The same is true for other valves. The actuator may be a pneumatic actuator or an electric actuator, or an actuator other than these. The control device 3 controls the actuator to open and close the liquid medicine valve 33.

[0094] The chemical liquid nozzle 31 is connected to a nozzle moving unit 34 that moves the chemical liquid nozzle 31 in at least one of a vertical direction and a horizontal direction. The nozzle moving unit 34 moves the chemical liquid nozzle 31 horizontally between a processing position where the chemical liquid ejected from the chemical liquid nozzle 31 is supplied to the upper surface of the substrate W and a standby position where the chemical liquid nozzle 31 is located around the processing cup 21 when viewed from above.

[0095] The rinse liquid nozzle 35 is connected to a rinse liquid pipe 36 that guides the rinse liquid to the rinse liquid nozzle 35. When the rinse liquid valve 37 installed on the rinse liquid pipe 36 is opened, the rinse liquid is continuously ejected downward from the ejection port of the rinse liquid nozzle 35. The rinse liquid ejected from the rinse liquid nozzle 35 is, for example, pure water (deionized water: DIW (Deionized Water)). The rinse liquid can be any of carbonated water, electrolytic ion water, hydrogen water, ozone water, hydrochloric acid water with a dilute concentration (for example, about 10 to 100 ppm), and ammonia water with a dilute concentration (for example, about 10 to 100 ppm).

[0096] The rinse liquid nozzle 35 is connected to a nozzle moving unit 38 that moves the rinse liquid nozzle 35 in at least one of a vertical direction and a horizontal direction. The nozzle moving unit 38 moves the rinse liquid nozzle 35 horizontally between a processing position where the rinse liquid sprayed from the rinse liquid nozzle 35 is supplied to the upper surface of the substrate W and a standby position where the rinse liquid nozzle 35 is located around the processing cup 21 when viewed from above.

[0097] The first liquid nozzle 39 is connected to a first liquid pipe 40 that guides the first liquid to the first liquid nozzle 39. When a first liquid valve 41 installed on the first liquid pipe 40 is opened, the first liquid is continuously ejected downward from the ejection port of the first liquid nozzle 39. The first liquid nozzle 39 is connected to a nozzle moving unit 42 that moves the first liquid nozzle 39 in at least one of a vertical direction and a horizontal direction. The nozzle moving unit 42 moves the first liquid nozzle 39 horizontally between a processing position, which is a position where the first liquid ejected from the first liquid nozzle 39 is supplied to the upper surface of the substrate W, and a standby position, which is a position where the first liquid nozzle 39 is located around the processing cup 21 when viewed from above.

[0098] The second liquid nozzle 43 is connected to a second liquid pipe 44 that guides the second liquid to the second liquid nozzle 43. When the second liquid valve 45 installed on the second liquid pipe 44 is opened, the second liquid is continuously ejected downward from the ejection port of the second liquid nozzle 43. The second liquid nozzle 43 is connected to a nozzle moving unit 46 that moves the second liquid nozzle 43 in at least one of a vertical direction and a horizontal direction. The nozzle moving unit 46 moves the second liquid nozzle 43 horizontally between a processing position, which is a position where the second liquid ejected from the second liquid nozzle 43 is supplied to the upper surface of the substrate W, and a standby position, which is a position where the second liquid nozzle 43 is located around the processing cup 21 when viewed from above.

[0099] The solubility of the second liquid in water is less than the solubility of the first liquid in water. The surface tension of the second liquid is lower than the surface tension of the first liquid. The specific gravity of the second liquid is greater than the specific gravity of the first liquid. The boiling point of the second liquid is above room temperature (for example, 20-25°C). The value obtained by subtracting room temperature from the boiling point of the second liquid is below room temperature. The value obtained by subtracting room temperature from the boiling point of the second liquid may also exceed room temperature. The boiling point of the second liquid may be lower than the boiling point of water. Similarly, the boiling point of the first liquid may also be lower than the boiling point of water. The boiling point of the second liquid may be above room temperature and below 50°C, or may be above 50°C. The vapor pressure of the second liquid may be higher than the vapor pressure of the first liquid. The surface tension of the first liquid may be lower than the surface tension of water.

[0100] Hereinafter, an example in which the first liquid is a liquid of IPA (also referred to as IPA for short) and the second liquid is a liquid of Novec (registered trademark) 7000 (also referred to as Novec 7000 for short) is described. Novec 7000 is a kind of HFE. The second liquid may also be a liquid of HFE other than Novec 7000, a liquid of a fluorine-based solvent other than HFE, or a liquid other than a fluorine-based solvent. The first liquid may also be a liquid of an alcohol other than IPA, such as propanol or methanol.

[0101] The solubility of Novec7000 in water is lower than that of IPA. The surface tension of Novec7000 is lower than that of IPA. The specific gravity of Novec7000 is greater than that of IPA. The boiling point of Novec7000 is 34°C. The boiling point of Novec7000 is above room temperature. When the room temperature is 23°C, the value obtained by subtracting the room temperature from the boiling point of Novec7000 is 11, which is below room temperature. The boiling point of Novec7000 is lower than that of IPA. The vapor pressure of Novec7000 is higher than that of IPA.

[0102] The processing unit 2 includes a blocking member 51 disposed above the spin chuck 10 . Figure 2 An example in which the blocking member 51 is a disk-shaped blocking plate is shown. The blocking member 51 includes a disk portion 52 horizontally arranged above the rotating chuck 10. The blocking member 51 is horizontally supported by a cylindrical support shaft 53 extending upward from the central portion of the disk portion 52. The center line of the disk portion 52 is arranged on the rotation axis A1 of the substrate W. The lower surface of the disk portion 52 is equivalent to the lower surface 51L of the blocking member 51. The lower surface 51L of the blocking member 51 is an opposite surface relative to the upper surface of the substrate W. The lower surface 51L of the blocking member 51 is parallel to the upper surface of the substrate W and has an outer diameter greater than the diameter of the substrate W.

[0103] The blocking member 51 is connected to a blocking member lifting unit 54 that vertically lifts and lowers the blocking member 51. The blocking member lifting unit 54 positions the blocking member 51 from the upper position ( Figure 2 The lower position is a close position where the lower surface 51L of the blocking member 51 approaches the upper surface of the substrate W to a height where a scanning nozzle such as the liquid medicine nozzle 31 cannot enter between the substrate W and the blocking member 51. The upper position is a far position where the blocking member 51 retreats to a height where a scanning nozzle can enter between the blocking member 51 and the substrate W.

[0104] The plurality of nozzles include a central nozzle 55 that ejects a processing fluid such as a processing liquid or a processing gas downward through an upper central opening 61 that opens in the central portion of the lower surface 51L of the blocking member 51. The central nozzle 55 extends in the up-down direction along the rotation axis A1. The central nozzle 55 is disposed in a through hole that penetrates the central portion of the blocking member 51 in the up-down direction. The inner circumferential surface of the blocking member 51 surrounds the outer circumferential surface of the central nozzle 55 at intervals in the radial direction (in a direction orthogonal to the rotation axis A1). The central nozzle 55 rises and falls together with the blocking member 51. The ejection port of the central nozzle 55 that ejects the processing fluid is disposed above the upper central opening 61 of the blocking member 51.

[0105] The central nozzle 55 is connected to an upper gas pipe 56 that guides the inert gas to the central nozzle 55. The substrate processing apparatus 1 may include a heater 59 that heats the inert gas ejected from the central nozzle 55. When the upper gas valve 57 installed on the upper gas pipe 56 is opened, the inert gas is continuously ejected downward from the ejection port of the central nozzle 55 at a flow rate corresponding to the opening of the flow rate regulating valve 58 that changes the flow rate of the inert gas. The inert gas ejected from the central nozzle 55 is nitrogen gas. The inert gas may also be a gas other than nitrogen gas, such as helium gas and argon gas.

[0106] The inner circumferential surface of the blocking member 51 and the outer circumferential surface of the center nozzle 55 form a cylindrical upper gas flow path 62 extending up and down. The upper gas flow path 62 is connected to an upper gas pipe 63 that guides the inert gas to the upper central opening 61 of the blocking member 51. When the upper gas valve 64 installed on the upper gas pipe 63 is opened, the inert gas is continuously ejected downward from the upper central opening 61 of the blocking member 51 at a flow rate corresponding to the opening of the flow regulating valve 65 that changes the flow rate of the inert gas. The inert gas ejected from the upper central opening 61 of the blocking member 51 is nitrogen. The inert gas may also be a gas other than nitrogen such as helium and argon.

[0107] The plurality of nozzles include a lower surface nozzle 71 that ejects a processing liquid toward the center of the lower surface of the substrate W. The lower surface nozzle 71 includes: a nozzle disk portion disposed between the upper surface 12u of the spin base 12 and the lower surface of the substrate W; and a nozzle cylindrical portion extending downward from the nozzle disk portion. The ejection port of the lower surface nozzle 71 opens at the center of the upper surface of the nozzle disk portion. When the substrate W is held by the spin chuck 10, the ejection port of the lower surface nozzle 71 is opposite to the center of the lower surface of the substrate W in the vertical direction.

[0108] The lower surface nozzle 71 is connected to a heating fluid pipe 72 for guiding warm water (pure water at a higher temperature than room temperature) as an example of a heating fluid to the lower surface nozzle 71. The pure water supplied to the lower surface nozzle 71 is heated by a heater 75 installed on the heating fluid pipe 72. When the heating fluid valve 73 installed on the heating fluid pipe 72 is opened, the warm water is continuously ejected upward from the ejection port of the lower surface nozzle 71 at a flow rate corresponding to the opening degree of the flow rate regulating valve 74 for changing the flow rate of the warm water. Thus, the warm water is supplied to the lower surface of the substrate W.

[0109] The outer peripheral surface of the lower surface nozzle 71 and the inner peripheral surface of the rotating base 12 form a cylindrical lower gas flow path 82 extending vertically. The lower gas flow path 82 includes a lower central opening 81 opened at the central portion of the upper surface 12u of the rotating base 12. The lower gas flow path 82 is connected to a lower gas piping 83 that guides the inert gas to the lower central opening 81 of the rotating base 12. When the lower gas valve 84 installed on the lower gas piping 83 is opened, the inert gas is continuously ejected upward from the lower central opening 81 of the rotating base 12 at a flow rate corresponding to the opening degree of the flow rate regulating valve 85 that changes the flow rate of the inert gas.

[0110] The inert gas ejected from the lower central opening 81 of the spin base 12 is nitrogen. The inert gas may be a gas other than nitrogen, such as helium or argon. When the substrate W is held by the spin chuck 10, if nitrogen is ejected from the lower central opening 81 of the spin base 12, the nitrogen flows radially between the lower surface of the substrate W and the upper surface 12u of the spin base 12. As a result, the space between the substrate W and the spin base 12 is filled with nitrogen.

[0111] Figure 3 2 is a block diagram showing the hardware of the control device 3 .

[0112] The control device 3 is a computer including a computer main body 3a and a peripheral device 3d connected to the computer main body 3a. The computer main body 3a includes a CPU 3b (central processing unit) for executing various commands and a main storage device 3c for storing information. The peripheral device 3d includes an auxiliary storage device 3e for storing information such as a program P, a reading device 3f for reading information from a removable medium RM, and a communication device 3g for communicating with other devices such as a host computer HC.

[0113] The control device 3 is connected to the input device and the display device. The input device is operated when an operator such as a user or a maintenance person in charge inputs information into the substrate processing device 1. The information is displayed on the screen of the display device. The input device can be any one of a keyboard, a pointing device, and a touch panel, or a device other than these. A touch panel display that serves as both an input device and a display device can also be provided in the substrate processing device 1.

[0114] The CPU 3b executes the program P stored in the auxiliary storage device 3e. The program P in the auxiliary storage device 3e may be pre-installed in the control device 3, or may be transferred to the auxiliary storage device 3e from the removable medium RM via the reading device 3f, or may be transferred to the auxiliary storage device 3e from an external device such as a host computer HC via the communication device 3g.

[0115] The auxiliary storage device 3e and the removable medium RM are non-volatile memories that retain storage even when power is not supplied. The auxiliary storage device 3e is a magnetic storage device such as a hard disk drive. The removable medium RM is a semiconductor memory such as an optical disk such as a CD or a memory card. The removable medium RM is an example of a computer-readable recording medium on which the program P is recorded. The removable medium RM is a non-temporary tangible recording medium.

[0116] The auxiliary storage device 3e stores a plurality of recipes. The recipe is information that specifies the processing content, processing conditions, and processing steps of the substrate W. The plurality of recipes differ from each other in at least one of the processing content, processing conditions, and processing steps of the substrate W. The control device 3 controls the substrate processing device 1 so that the substrate W is processed according to the recipe specified by the host computer HC. The control device 3 is programmed so as to execute the following steps.

[0117] Next, the first embodiment will be described.

[0118] Figure 4 The following are process diagrams for explaining an example (first embodiment) of processing of a substrate W performed by the substrate processing apparatus 1. Figure 5A to Figure 5C FIG. 2 is a schematic diagram showing the state of the substrate W when the first embodiment is performed. Figure 2 and Figure 4 .for Figure 5A to Figure 5C , with appropriate reference.

[0119] The substrate W to be processed is, for example, a semiconductor wafer such as a silicon wafer. The surface of the substrate W corresponds to a device forming surface on which devices such as transistors and capacitors are formed. The substrate W may be a substrate having a pattern P1 formed on the surface of the substrate W as a pattern forming surface (see Fig.14A ) may be a substrate W having no pattern P1 formed on the surface of the substrate W. In the latter case, the pattern P1 may be formed in a chemical solution supplying step described later.

[0120] When the substrate W is processed by the substrate processing apparatus 1, a loading step ( Figure 4 Step S1).

[0121] Specifically, when the blocking member 51 is located at the upper position, all the protective covers 24 are located at the lower position, and all the scanning nozzles are located at the standby position, the central robot CR (see Figure 1A) The central robot CR supports the substrate W with the hand H1 and causes the hand H1 to enter the chamber 4. Then, the central robot CR places the substrate W on the hand H1 on the plurality of chuck pins 11 with the surface of the substrate W facing upward. Thereafter, the plurality of chuck pins 11 are pressed against the outer peripheral surface of the substrate W to hold the substrate W. After placing the substrate W on the spin chuck 10, the central robot CR causes the hand H1 to withdraw from the interior of the chamber 4.

[0122] Next, the upper gas valve 64 and the lower gas valve 84 are opened, and nitrogen begins to be ejected from the upper central opening 61 of the blocking member 51 and the lower central opening 81 of the spin base 12. As a result, the space between the substrate W and the blocking member 51 is filled with nitrogen. Similarly, the space between the substrate W and the spin base 12 is filled with nitrogen. On the other hand, the protective cover lifting unit 27 raises at least one protective cover 24 from the lower position to the upper position. Thereafter, the rotation motor 14 is driven to cause the substrate W to start rotating ( Figure 4 Thus, the substrate W is rotated at a chemical solution supply speed (100 rpm or more and less than 1000 rpm).

[0123] Next, the drug solution supply process is performed ( Figure 4 In step S3), the chemical solution is supplied to the upper surface of the substrate W to form a liquid film of the chemical solution covering the entire area of ​​the upper surface of the substrate W.

[0124] Specifically, when the blocking member 51 is located at the upper position and at least one protective cover 24 is located at the upper position, the nozzle moving unit 34 moves the liquid medicine nozzle 31 from the standby position to the processing position. Thereafter, the liquid medicine valve 33 is opened, and the liquid medicine nozzle 31 starts to spray the liquid medicine. When a predetermined time has passed since the liquid medicine valve 33 was opened, the liquid medicine valve 33 is closed, and the spraying of the liquid medicine is stopped. Thereafter, the nozzle moving unit 34 moves the liquid medicine nozzle 31 to the standby position.

[0125] The chemical liquid ejected from the chemical liquid nozzle 31 collides with the upper surface of the substrate W rotating at the chemical liquid supply speed, and then flows outward along the upper surface of the substrate W due to the centrifugal force. Therefore, the chemical liquid is supplied to the entire upper surface of the substrate W, and a liquid film of the chemical liquid covering the entire upper surface of the substrate W is formed. When the chemical liquid nozzle 31 ejects the chemical liquid, the nozzle moving unit 34 may move the chemical liquid landing position relative to the upper surface of the substrate W so that the chemical liquid passes through the central portion and the outer peripheral portion, or may keep the chemical liquid landing position stationary at the central portion.

[0126] Next, the rinsing liquid supply process is performed ( Figure 4 In step S4), pure water as an example of a rinsing liquid is supplied to the upper surface of the substrate W, thereby washing away the chemical liquid on the substrate W.

[0127] Specifically, when the blocking member 51 is located at the upper position and at least one protective cover 24 is located at the upper position, the nozzle moving unit 38 moves the rinsing liquid nozzle 35 from the standby position to the processing position. Thereafter, the rinsing liquid valve 37 is opened, and the rinsing liquid nozzle 35 starts to spray the rinsing liquid. Before starting to spray the pure water, in order to switch the protective cover 24 that blocks the liquid discharged from the substrate W, the protective cover lifting unit 27 can move at least one protective cover 24 vertically. When a predetermined time has passed since the rinsing liquid valve 37 was opened, the rinsing liquid valve 37 is closed to stop spraying the rinsing liquid. Thereafter, the nozzle moving unit 38 moves the rinsing liquid nozzle 35 to the standby position.

[0128] After the pure water ejected from the rinse liquid nozzle 35 collides with the upper surface of the substrate W rotating at the rinse liquid supply speed (100 rpm or more and less than 1000 rpm), it flows outward along the upper surface of the substrate W due to the centrifugal force. The chemical liquid on the substrate W is replaced by the pure water ejected from the rinse liquid nozzle 35. Thus, a liquid film of pure water covering the entire area of ​​the upper surface of the substrate W is formed. When the rinse liquid nozzle 35 ejects pure water, the nozzle moving unit 38 can move the liquid landing position relative to the upper surface of the substrate W so that the pure water passes through the central part and the peripheral part, or can keep the liquid landing position stationary at the central part.

[0129] Next, the first replacement step ( Figure 4 In step S5), the first liquid is supplied to the upper surface of the substrate W, and the rinsing liquid on the upper surface of the substrate W is replaced by the first liquid.

[0130] Specifically, when the blocking member 51 is located at the upper position and at least one protective cover 24 is located at the upper position, the nozzle moving unit 42 moves the first liquid nozzle 39 from the standby position to the processing position. Thereafter, the spin chuck 10 rotates the substrate W at the first replacement speed. The first replacement speed may be equal to or different from the rinsing liquid supply speed. When the first liquid nozzle 39 is located above the substrate W, the first liquid valve 41 is opened, and the first liquid nozzle 39 starts to eject the first liquid. Before the first liquid is ejected, in order to switch the protective cover 24 that blocks the liquid discharged from the substrate W, the protective cover lifting unit 27 may vertically move at least one protective cover 24.

[0131] The first liquid ejected from the first liquid nozzle 39 collides with the upper surface of the substrate W rotating at the first replacement speed, and then flows outward along the upper surface of the substrate W. The pure water on the substrate W is replaced by the first liquid ejected from the first liquid nozzle 39. Thus, a first liquid film F1 (liquid film of the first liquid, the same below) covering the entire area of ​​the upper surface of the substrate W is formed. When the first liquid nozzle 39 ejects the first liquid, the nozzle moving unit 42 can move the liquid landing position relative to the upper surface of the substrate W in such a manner that the first liquid passes through the central part and the peripheral part, or can keep the liquid landing position stationary at the central part.

[0132] After the pure water liquid film is replaced by the first liquid film F1, the first immersion step ( Figure 4 Step S6), that is, stopping the discharge of the first liquid and maintaining the first liquid film F1 on the upper surface of the substrate W.

[0133] Specifically, when the first liquid nozzle 39 is stationary at the central processing position where the first liquid ejected from the first liquid nozzle 39 collides with the central portion of the upper surface of the substrate W, the spin chuck 10 reduces the rotation speed of the substrate W from the first replacement speed to the first immersion speed. The first immersion speed is, for example, a speed greater than 0 and less than 50 rpm. After the rotation speed of the substrate W is reduced to the first immersion speed, the first liquid valve 41 is closed to stop ejecting the first liquid. Thereafter, the nozzle moving unit 42 moves the first liquid nozzle 39 from the central processing position to the standby position.

[0134] If the rotation speed of the substrate W is reduced to the first immersion speed, the centrifugal force of the first liquid applied to the substrate W is weakened. Therefore, the first liquid is not discharged from the upper surface of the substrate W, or only a small amount is discharged. Therefore, after the ejection of the first liquid is stopped, the first liquid film F1 covering the entire area of ​​the upper surface of the substrate W is also maintained on the substrate W. Even after the liquid film of pure water is replaced by the first liquid film F1, a small amount of pure water remains in the pattern P1 (see Fig.14A ), the pure water will also dissolve in the first liquid and diffuse in the first liquid. Thus, the pure water remaining between the patterns P1 can be reduced.

[0135] Next, the second replacement step ( Figure 4 In step S7-1), the second liquid is supplied to the upper surface of the substrate W, and the first liquid on the upper surface of the substrate W is replaced by the second liquid.

[0136] Specifically, when the blocking member 51 is located at the upper position and at least one protective cover 24 is located at the upper position, the nozzle moving unit 46 moves the second liquid nozzle 43 from the standby position to the processing position. Thereafter, the spin chuck 10 rotates the substrate W at the second replacement speed. The second replacement speed may be equal to or different from the rinsing liquid supply speed. The second replacement speed may be equal to or different from the first replacement speed. When the second liquid nozzle 43 is located above the substrate W, the second liquid valve 45 is opened, and the second liquid nozzle 43 starts to eject the second liquid. Before the second liquid is ejected, in order to switch the protective cover 24 that blocks the liquid discharged from the substrate W, the protective cover lifting unit 27 may move at least one protective cover 24 vertically.

[0137] The second liquid ejected from the second liquid nozzle 43 collides with the upper surface of the substrate W rotating at the second replacement speed, and then flows outward along the upper surface of the substrate W. When the second liquid nozzle 43 ejects the second liquid, the nozzle moving unit 46 may move the liquid landing position with respect to the upper surface of the substrate W so that the second liquid passes through the central portion and the peripheral portion, or may keep the liquid landing position stationary at the central portion. In this example, the nozzle moving unit 46 keeps the second liquid nozzle 43 stationary at the central processing position where the second liquid ejected from the second liquid nozzle 43 collides with the central portion of the upper surface of the substrate W.

[0138] If the second liquid nozzle 43 ejects the second liquid toward the central portion of the upper surface of the substrate W, the second liquid ejected from the second liquid nozzle 43 collides with the first liquid film F1 at the central portion of the upper surface of the substrate W. The second liquid penetrates the first liquid film F1 and collides with the central portion of the upper surface of the substrate W. The first liquid located at the central portion of the upper surface of the substrate W is washed outward along the upper surface of the substrate W by the supply of the second liquid. The second liquid that collides with the central portion of the upper surface of the substrate W flows outward in all directions along the upper surface of the substrate W from the central portion of the upper surface of the substrate W. Thus, as shown in FIG. Figure 5A As shown, on the upper surface of the substrate W, there are formed a substantially circular second liquid film F2 (liquid film of the second liquid, hereinafter the same) covering the central portion of the upper surface of the substrate W, and an annular first liquid film F1 surrounding the second liquid film F2.

[0139] The specific gravity of the second liquid is greater than that of the first liquid. Therefore, at the interface between the first liquid and the second liquid, the second liquid moves toward the upper surface of the substrate W due to gravity, and the first liquid moves above the second liquid. That is, due to the difference in specific gravity, the second liquid enters between the first liquid and the substrate W (see Figure 5A). If the second liquid is continuously ejected, such an interface moves outward along the upper surface of the substrate W. Therefore, the first liquid remaining between the second liquid and the substrate W can be reduced, and the first liquid can be replaced with the second liquid reliably. As a result, the first liquid remaining in the pattern P1 (see Fig.14A ) between the first liquid.

[0140] If the second liquid is continuously ejected, the outer diameter of the second liquid film F2 gradually increases, and the width of the annular first liquid film F1 (the radial length from the inner periphery of the first liquid film F1 to the outer peripheral surface of the substrate W) gradually decreases. When a predetermined time has passed since the start of ejection of the second liquid, the outer periphery of the second liquid film F2 extends to the outer periphery of the upper surface of the substrate W, and all or almost all of the first liquid is replaced by the second liquid. Figure 5B As shown, the second liquid film F2 is formed to cover the entire upper surface of the substrate W. Thereafter, the second liquid valve 45 is closed to stop the discharge of the second liquid.

[0141] The second liquid is supplied to the upper surface of the substrate W rotating at the second replacement speed. In this example, the second replacement speed is smaller than the rinsing liquid supply speed and is equal to the first immersion speed (for example, a speed greater than 0 and less than 50 rpm). That is, the second liquid is ejected toward the upper surface of the substrate W rotating at a low speed. As described above, if the ejection of the second liquid is continued, the outer diameter of the second liquid film F2 gradually increases. If the second liquid is continuously ejected toward the upper surface of the substrate W rotating at a low speed, the outer periphery of the second liquid film F2 expands to the outer periphery of the upper surface of the substrate W while maintaining a substantially circular state.

[0142] On the other hand, when the properties of the first liquid and the second liquid are greatly different, if the second liquid is continuously ejected toward the upper surface of the substrate W rotating at a high speed, there is a concern that the first liquid may remain on the outer peripheral portion of the upper surface of the substrate W. For example, there is a concern that the outer periphery of the second liquid film F2 may become jagged in the outer periphery of the upper surface of the substrate W when viewed from above, and the first liquid may remain between the jagged outer peripheries of the second liquid film F2. In the case of such a concern, as described above, the second liquid may be continuously ejected toward the upper surface of the substrate W rotating at a low speed.

[0143] The rotating chuck 10 rotates the substrate W at a second replacement speed while the ejection of the second liquid is stopped, while the second liquid film F2 covering the entire area of ​​the upper surface of the substrate W is maintained. As described above, in this example, the second replacement speed is equal to the first immersion speed. When the second replacement speed is equal to the first immersion speed, the second liquid is not discharged from the upper surface of the substrate W, or only a very small amount is discharged. Therefore, when the ejection of the second liquid is stopped, the second liquid film F2 covering the entire area of ​​the upper surface of the substrate W is maintained on the upper surface of the substrate W (second immersion step ( Figure 4 Step S8-1)).

[0144] Even if a trace amount of the first liquid remains between the second liquid film F2 and the substrate W after the first liquid film F1 is replaced by the second liquid film F2, the first liquid will dissolve in the second liquid and diffuse in the second liquid. Thus, the first liquid remaining between the second liquid film F2 and the substrate W can be reduced. After the ejection of the second liquid is stopped, if the second liquid film F2 is kept on the upper surface of the substrate W, the time for the first liquid to dissolve in the second liquid can be extended, and more of the first liquid can be dissolved in the second liquid.

[0145] Next, the drying process is performed ( Figure 4 In step S11), the substrate W is dried by rotating the substrate W at a high speed.

[0146] Specifically, the blocking member lifting unit 54 lowers the blocking member 51 from the upper position to the lower position. In this state, the spin chuck 10 rotates the substrate W at a high rotation speed (e.g., several thousand rpm) that is higher than the supply speed of the rinsing liquid. The second liquid on the upper surface of the substrate W flows outward along the upper surface of the substrate W in a disorderly manner. Figure 5C As shown in FIG. 1 , the second liquid is removed from the substrate W, and the substrate W is dried. When a predetermined time has passed since the substrate W started to rotate at a high speed, the spin chuck 10 stops rotating. Thus, the rotation of the substrate W is stopped ( Figure 4 Step S12).

[0147] Next, carry out the unloading process ( Figure 4 Step S13), that is, moving the substrate W out of the chamber 4.

[0148] Specifically, the blocking member lifting unit 54 raises the blocking member 51 to the upper position, and the protective cover lifting unit 27 lowers all the protective covers 24 to the lower position. Then, the upper gas valve 64 and the lower gas valve 84 are closed, and the upper central opening 61 of the blocking member 51 and the lower central opening 81 of the rotating base 12 stop spraying nitrogen. Thereafter, the central robot CR causes the hand H1 to enter the chamber 4. After the central robot CR releases the grip of the substrate W by the plurality of chuck pins 11, the central robot CR supports the substrate W on the rotating chuck 10 with the hand H1. Thereafter, the central robot CR supports the substrate W with the hand H1 while withdrawing the hand H1 from the interior of the chamber 4. Thus, the processed substrate W is carried out of the chamber 4.

[0149] Next, the second embodiment will be described.

[0150] From the loading process ( Figure 6 Step S1) to the first immersion step ( Figure 6The process of the second embodiment up to step S6) is the same as that of the first embodiment, and therefore, the process after the second replacement step will be described below.

[0151] Figure 6 The following are process diagrams for explaining another example (second embodiment) of processing of the substrate W performed by the substrate processing apparatus 1. Figure 7A to Figure 7F FIG. 2 is a schematic diagram showing the state of the substrate W when the second embodiment is performed. Figure 2 and Figure 6 .for Figure 7A to Figure 7F , with appropriate reference.

[0152] After the first liquid film F1 is formed, the second replacement step ( Figure 6 In step S7-2), the second liquid is supplied to the upper surface of the substrate W, and the first liquid on the upper surface of the substrate W is replaced by the second liquid.

[0153] Specifically, when the blocking member 51 is located at the upper position and at least one protective cover 24 is located at the upper position, the nozzle moving unit 46 moves the second liquid nozzle 43 from the standby position to the processing position. Thereafter, the spin chuck 10 rotates the substrate W at the second replacement speed. The second replacement speed may be equal to or different from the rinse liquid supply speed. The second replacement speed may be equal to or different from the first replacement speed. When the second liquid nozzle 43 is located above the substrate W, the second liquid valve 45 is opened, and the second liquid nozzle 43 starts to spray the second liquid.

[0154] Before the second liquid is ejected, the shield lifting unit 27 may vertically move at least one shield 24 in order to switch the shield 24 that blocks the liquid discharged from the substrate W. When the second liquid nozzle 43 ejects the second liquid, the nozzle moving unit 46 may move the liquid landing position with respect to the upper surface of the substrate W so that the second liquid passes through the central portion and the peripheral portion, or may keep the liquid landing position stationary at the central portion. In this example, the nozzle moving unit 46 keeps the second liquid nozzle 43 stationary at the central processing position where the second liquid ejected from the second liquid nozzle 43 collides with the central portion of the upper surface of the substrate W.

[0155] like Fig. 7A As shown in FIG. 1 , if the second liquid is ejected toward the center of the upper surface of the substrate W, a roughly circular second liquid film F2 covering the center of the upper surface of the substrate W and an annular first liquid film F1 surrounding the second liquid film F2 are formed on the upper surface of the substrate W. If the ejection of the second liquid is continued, the outer diameter of the second liquid film F2 gradually increases, and the width of the annular first liquid film F1 gradually decreases. The second liquid valve 45 is closed before the first liquid film F1 disappears from the upper surface of the substrate W. As shown in FIG. 1 , the second liquid valve 45 is closed before the first liquid film F1 disappears from the upper surface of the substrate W. Figure 7BAs shown, for example, the total amount of the second liquid ejected from the second liquid nozzle 43 is controlled so that the first liquid film F1 remains only on the outer peripheral portion of the upper surface of the substrate W. The width of the first liquid film F1 is smaller than the radius of the second liquid film F2.

[0156] The spin chuck 10 rotates the substrate W, which maintains the roughly circular second liquid film F2 and the annular first liquid film F1, at a second replacement speed while stopping the ejection of the second liquid. The second replacement speed may be equal to the first immersion speed (for example, a speed greater than 0 and less than 50 rpm). When the second replacement speed is equal to the first immersion speed, the first liquid is not discharged from the upper surface of the substrate W, or only a small amount is discharged. Therefore, if Figure 7B As shown, in the state where the ejection of the second liquid is stopped, the substantially circular second liquid film F2 and the annular first liquid film F1 are maintained on the upper surface of the substrate W (second immersion step ( Figure 6 Step S8-2)).

[0157] If the outer periphery of the second liquid film F2 is extended to the outer periphery of the upper surface of the substrate W in such a manner that the annular first liquid film F1 does not remain on the outer periphery of the upper surface of the substrate W, a thin second liquid film F2 is formed on the upper surface of the substrate W. This is because the surface tension of the second liquid is low. In addition, since the second liquid film F2 is not only thin but also highly volatile, if the ejection of the second liquid is stopped, the second liquid on the substrate W may evaporate rapidly, and a part of the upper surface of the substrate W may be exposed from the second liquid film F2 in a short time.

[0158] In contrast, since the surface tension of the first liquid is higher than that of the second liquid, the thickness of the first liquid film F1 remaining on the outer periphery of the upper surface of the substrate W is greater than the thickness of the second liquid film F2. The second liquid supplied to the upper surface of the substrate W is retained inside the annular first liquid film F1. Therefore, compared with the case where the outer periphery of the second liquid film F2 is extended to the outer periphery of the upper surface of the substrate W, a thicker second liquid film F2 is formed inside the first liquid film F1. Thus, it is possible to prevent a portion of the upper surface of the substrate W from being exposed from the second liquid film F2 in a short time.

[0159] Next, a liquid discharge step is performed to form an exposure hole H in the second liquid film F2 so that the central portion of the upper surface of the substrate W is exposed from the second liquid film F2 , and the outer edge of the exposure hole H is extended to the outer periphery of the upper surface of the substrate W.

[0160] Specifically, when the blocking member 51 is in the upper position and at least one protective cover 24 is in the upper position, the heating fluid valve 73 is opened, and the lower surface nozzle 71 starts to spray warm water (for example, 45 to 60° C.) as an example of a heating fluid. The spraying of warm water may be started before or after the second liquid is supplied to the upper surface of the substrate W, or may be started at the same time as the second liquid is supplied to the upper surface of the substrate W. The spraying of warm water stops after the outer edge of the exposure hole H extends to the outer periphery of the upper surface of the substrate W. If the exposure hole H is formed, the spraying of warm water may also stop before the outer edge of the exposure hole H extends to the outer periphery of the upper surface of the substrate W.

[0161] In addition, the spin chuck 10 rotates the substrate W at a liquid discharge speed. The liquid discharge speed is greater than the first immersion speed. The liquid discharge speed may be equal to or different from the second replacement speed. In this example, the liquid discharge speed is a speed greater than the first immersion speed and less than the rinse liquid supply speed. When the liquid discharge speed is different from the second replacement speed, the rotation speed of the substrate W may be changed before or after the start of the warm water spraying, or may be changed at the same time as the start of the warm water spraying. In addition, before the start of the warm water spraying, in order to switch the protective cover 24 that blocks the liquid discharged from the substrate W, the protective cover lifting unit 27 may move at least one protective cover 24 vertically.

[0162] like Figure 7C As shown in FIG. 1 , the lower surface nozzle 71 sprays warm water toward the center of the lower surface of the substrate W while the spraying of the second liquid toward the substrate W has stopped and the substantially circular second liquid film F2 and the annular first liquid film F1 are maintained on the upper surface of the substrate W. The warm water sprayed upward from the lower surface nozzle 71 collides with the center of the lower surface of the substrate W and then flows outward along the rotating lower surface of the substrate W. Thus, the warm water is supplied to the entire area of ​​the lower surface of the substrate W, and the entire area of ​​the substrate W is heated. The first liquid and the second liquid on the upper surface of the substrate W are indirectly heated via the substrate W.

[0163] The heating of the first liquid and the second liquid promotes the evaporation of the first liquid and the second liquid. The warm water sprayed from the lower surface nozzle 71 first collides with the central portion of the lower surface of the substrate W. Therefore, the heat transferred from the warm water to the substrate W increases as it approaches the central portion of the lower surface of the substrate W. The evaporation rate of the second liquid is the highest at the central portion of the upper surface of the substrate W. Therefore, Fig.7D As shown in FIG. 1 , a substantially circular exposure hole H is formed penetrating the central portion of the second liquid film F2 (hole forming step ( Figure 6 In step S9-2), the second liquid film F2 changes into a ring shape. As a result, the center portion of the upper surface of the substrate W is exposed from the second liquid film F2.

[0164] After the exposure hole H is formed in the central portion of the second liquid film F2, the second liquid forming the inner periphery of the annular second liquid film F2 evaporates. As a result, the inner diameter of the second liquid film F2 corresponding to the diameter of the exposure hole H expands. In addition, the second liquid on the upper surface of the substrate W flows outward along the upper surface of the substrate W due to the centrifugal force, and the inner and outer diameters of the second liquid film F2 expand. The first liquid on the outer periphery of the upper surface of the substrate W is pushed outward by the second liquid and discharged from the substrate W. As a result, Fig. 7E As shown in FIG. 1 , the first liquid film F1 is discharged from the substrate W. Thereafter, as shown in FIG. Figure 7F As shown, the inner periphery of the second liquid film F2 extends to the outer periphery of the upper surface of the substrate W (hole enlarging step ( Figure 6 In step S10-2), the second liquid film F2 is discharged from the substrate W. As a result, droplets of a size that can be visually observed disappear from the upper surface of the substrate W, and the entire area of ​​the upper surface of the substrate W is exposed.

[0165] The temperature of the warm water may be any value as long as it is higher than the room temperature and is a value below the boiling point of water. The temperature of the warm water may be above the boiling point of the second liquid. For example, the temperature of the warm water may be a temperature slightly higher than the boiling point of the second liquid. Specifically, the value obtained by subtracting the boiling point of the second liquid from the temperature of the warm water may be below the room temperature. When the temperature of the warm water is above the boiling point of the second liquid, at least the central portion of the upper surface of the substrate W is heated to a temperature above the boiling point of the second liquid.

[0166] When the temperature of the warm water is slightly higher than the boiling point of the second liquid, the second liquid is vaporized at least at the center of the upper surface of the substrate W, and a large number of small bubbles are interposed between the second liquid and the upper surface of the substrate W. When the warm water is ejected before the supply of the second liquid begins, the second liquid enters between the first liquid and the substrate W due to the difference in specific gravity, and vaporizes on the upper surface of the substrate W immediately after being supplied to the substrate W (for example, within 5 seconds after being supplied to the substrate W).

[0167] When the second liquid is vaporized at the interface between the second liquid film F2 and the substrate W, a vapor layer containing the vapor of the second liquid is formed between the second liquid film F2 and the substrate W (see Fig.14A ), the second liquid leaves the upper surface of the substrate W. In this case, if the thickness of the vapor layer is greater than the height of the pattern P1, all of the second liquid disappears from between the patterns P1. Therefore, the second liquid film F2 can be discharged from the substrate W while preventing the pattern P1 from collapsing.

[0168] Next, the drying process is performed ( Figure 6 In step S11), the substrate W is dried by rotating the substrate W at a high speed.

[0169] Specifically, the blocking member lifting unit 54 lowers the blocking member 51 from the upper position to the lower position. In this state, the spin chuck 10 rotates the substrate W at a high rotation speed (for example, several thousand rpm) that is greater than the supply speed of the rinsing liquid. Even if droplets of a size that cannot be visually observed remain on the upper surface of the substrate W (for example, between the patterns P1), such droplets will evaporate during the period when the substrate W rotates at a high speed. Thus, the substrate W is dried. After a predetermined time has passed since the substrate W started to rotate at a high speed, the spin chuck 10 stops rotating. Thus, the rotation of the substrate W is stopped ( Figure 6 Step S12).

[0170] Next, carry out the unloading process ( Figure 6 Step S13), that is, moving the substrate W out of the chamber 4.

[0171] Specifically, the blocking member lifting unit 54 raises the blocking member 51 to the upper position, and the protective cover lifting unit 27 lowers all the protective covers 24 to the lower position. Then, the upper gas valve 64 and the lower gas valve 84 are closed, and the upper central opening 61 of the blocking member 51 and the lower central opening 81 of the rotating base 12 stop spraying nitrogen. Thereafter, the central robot CR causes the hand H1 to enter the chamber 4. After the central robot CR releases the grip of the substrate W by the plurality of chuck pins 11, the central robot CR supports the substrate W on the rotating chuck 10 with the hand H1. Thereafter, the central robot CR supports the substrate W with the hand H1 while withdrawing the hand H1 from the interior of the chamber 4. Thus, the processed substrate W is carried out of the chamber 4.

[0172] Next, the third embodiment will be described.

[0173] From the loading process ( Figure 8 Step S1) to the first immersion step ( Figure 8 The process of the third embodiment up to step S6) is the same as that of the first embodiment, so the process after the second replacement step will be described below.

[0174] Figure 8 The following are process diagrams for explaining another example (third embodiment) of processing of the substrate W performed by the substrate processing apparatus 1. Figures 9A to 9C FIG. 2 is a schematic diagram showing the state of the substrate W when the third embodiment is performed. Figure 2 and Figure 8 .for Figures 9A to 9C , with appropriate reference.

[0175] After the first liquid film F1 is formed, the second replacement step ( Figure 8 In step S7-3), the second liquid is supplied to the upper surface of the substrate W, and the first liquid on the upper surface of the substrate W is replaced by the second liquid.

[0176] Specifically, when the blocking member 51 is located at the upper position and at least one protective cover 24 is located at the upper position, the nozzle moving unit 46 moves the second liquid nozzle 43 from the standby position to the processing position. Thereafter, the spin chuck 10 rotates the substrate W at the second replacement speed. The second replacement speed may be equal to or different from the rinse liquid supply speed. The second replacement speed may be equal to or different from the first replacement speed. When the second liquid nozzle 43 is located above the substrate W, the second liquid valve 45 is opened, and the second liquid nozzle 43 starts to spray the second liquid.

[0177] Before the second liquid is ejected, the shield lifting unit 27 may vertically move at least one shield 24 in order to switch the shield 24 that blocks the liquid discharged from the substrate W. When the second liquid nozzle 43 ejects the second liquid, the nozzle moving unit 46 may move the liquid landing position with respect to the upper surface of the substrate W so that the second liquid passes through the central portion and the peripheral portion, or may keep the liquid landing position stationary at the central portion. In this example, the nozzle moving unit 46 keeps the second liquid nozzle 43 stationary at the central processing position where the second liquid ejected from the second liquid nozzle 43 collides with the central portion of the upper surface of the substrate W.

[0178] If the second liquid is ejected toward the center of the upper surface of the substrate W, a substantially circular second liquid film F2 covering the center of the upper surface of the substrate W and an annular first liquid film F1 surrounding the second liquid film F2 are formed on the upper surface of the substrate W. If the ejection of the second liquid is continued, the outer diameter of the second liquid film F2 gradually increases, and the width of the annular first liquid film F1 gradually decreases. When a predetermined time has passed since the second liquid valve 45 was opened, the outer periphery of the second liquid film F2 extends to the outer periphery of the upper surface of the substrate W, and all or almost all of the first liquid is replaced by the second liquid.

[0179] After the central part of the upper surface of the substrate W is covered by the second liquid film F2, a liquid discharge process is performed, that is, an exposure hole H is formed on the second liquid film F2 to expose the central part of the upper surface of the substrate W from the second liquid film F2, and the outer edge of the exposure hole H is extended to the periphery of the upper surface of the substrate W.

[0180] Specifically, in a state where the second liquid nozzle 43 is ejecting the second liquid, the nozzle moving unit 46 moves the second liquid nozzle 43 from the central processing position to the peripheral processing position. The central processing position is a position where the second liquid ejected from the second liquid nozzle 43 collides with the central portion of the upper surface of the substrate W. The peripheral processing position is a peripheral processing position where the second liquid ejected from the second liquid nozzle 43 collides with the peripheral portion of the upper surface of the substrate W.

[0181] The nozzle moving unit 46 may move the second liquid nozzle 43 from the central processing position to the peripheral processing position at a constant speed, or may move the second liquid nozzle 43 from the central processing position to the peripheral processing position while changing the moving speed of the second liquid nozzle 43. In addition, the movement of the second liquid nozzle 43 may start before or after the periphery of the second liquid film F2 extends to the periphery of the upper surface of the substrate W, or may start at the same time as the periphery of the second liquid film F2 extends to the periphery of the upper surface of the substrate W. Fig.9A An example in which the second liquid nozzle 43 moves from the central processing position before the outer periphery of the second liquid film F2 spreads to the outer periphery of the upper surface of the substrate W is shown.

[0182] The spin chuck 10 rotates the substrate W at a liquid discharge speed. The liquid discharge speed is greater than the first immersion speed. The liquid discharge speed may be equal to or different from the second replacement speed. In this example, the liquid discharge speed is a speed greater than the first immersion speed and less than the rinse liquid supply speed. When the liquid discharge speed is different from the second replacement speed, the rotation speed of the substrate W may be changed before or after the second liquid nozzle 43 starts to move, or may be changed at the same time as the second liquid nozzle 43 starts to move.

[0183] After the second liquid nozzle 43 leaves the central processing position, the second liquid ejected from the second liquid nozzle 43 is not supplied to the central portion of the upper surface of the substrate W. In other words, no new second liquid is supplied to the central portion of the upper surface of the substrate W. The existing second liquid at the central portion of the upper surface of the substrate W evaporates. Fig. 9B As shown in FIG. 1 , after a while from the time when the second liquid nozzle 43 leaves the central processing position, a substantially circular exposure hole H penetrating the central portion of the second liquid film F2 is formed (hole forming step ( Figure 8 In step S9-3), the second liquid film F2 changes into a ring shape. As a result, the center portion of the upper surface of the substrate W is exposed from the second liquid film F2.

[0184] right Fig. 9B and Fig. 9C By comparison, it can be seen that the inner diameter of the second liquid film F2, which corresponds to the diameter of the exposure hole H, increases as the second liquid nozzle 43 moves away from the central processing position. In the case where the annular first liquid film F1 exists around the second liquid film F2, the width of the first liquid film F1 decreases as the second liquid nozzle 43 moves away from the central processing position. The entire first liquid constituting the first liquid film F1 is discharged from the substrate W before the second liquid nozzle 43 reaches the peripheral processing position.

[0185] In addition, when the second liquid nozzle 43 reaches the peripheral processing position, the second liquid valve 45 is closed to stop ejecting the second liquid. Thereafter, the nozzle moving unit 46 moves the second liquid nozzle 43 to the standby position. After the ejection of the second liquid is stopped, the annular second liquid film F2 remains on the peripheral portion of the upper surface of the substrate W, and only the peripheral portion of the upper surface of the substrate W is covered with the second liquid. The annular second liquid film F2 remaining on the upper surface of the substrate W after the ejection of the second liquid is stopped is discharged from the upper surface of the substrate W due to centrifugal force (hole enlargement process ( Figure 8 Step S10-3)). As a result, droplets of a size that can be visually observed disappear from the upper surface of the substrate W, and the entire area of ​​the upper surface of the substrate W is exposed.

[0186] Next, the drying process is performed ( Figure 8 In step S11), the substrate W is dried by rotating the substrate W at a high speed.

[0187] Specifically, the blocking member lifting unit 54 lowers the blocking member 51 from the upper position to the lower position. In this state, the spin chuck 10 rotates the substrate W at a high rotation speed (for example, several thousand rpm) that is greater than the supply speed of the rinsing liquid. Even if droplets of a size that cannot be visually observed remain on the upper surface of the substrate W (for example, between the patterns P1), such droplets will evaporate during the period when the substrate W rotates at a high speed. Thus, the substrate W is dried. After a predetermined time has passed since the substrate W started to rotate at a high speed, the spin chuck 10 stops rotating. Thus, the rotation of the substrate W is stopped ( Figure 8 Step S12).

[0188] Next, carry out the unloading process ( Figure 8 Step S13), that is, moving the substrate W out of the chamber 4.

[0189] Specifically, the blocking member lifting unit 54 raises the blocking member 51 to the upper position, and the protective cover lifting unit 27 lowers all the protective covers 24 to the lower position. Then, the upper gas valve 64 and the lower gas valve 84 are closed, and the upper central opening 61 of the blocking member 51 and the lower central opening 81 of the rotating base 12 stop spraying nitrogen. Thereafter, the central robot CR causes the hand H1 to enter the chamber 4. After the central robot CR releases the grip of the substrate W by the plurality of chuck pins 11, the central robot CR supports the substrate W on the rotating chuck 10 with the hand H1. Thereafter, the central robot CR supports the substrate W with the hand H1 while withdrawing the hand H1 from the interior of the chamber 4. Thus, the processed substrate W is carried out of the chamber 4.

[0190] Next, a fourth embodiment will be described.

[0191] From the loading process ( Fig.10 Step S1) to the second immersion step ( Fig.10 The process of the fourth embodiment up to step S8-3) is the same as that of the third embodiment, and therefore, the process after the liquid discharge step will be described below.

[0192] Fig.10 The following are process diagrams for explaining another example (fourth embodiment) of processing of the substrate W performed by the substrate processing apparatus 1. Figures 11A to 11C FIG. 2 is a schematic diagram showing the state of the substrate W when the fourth embodiment is performed. Figure 2 and Fig.10 .for Figures 11A to 11C , with appropriate reference.

[0193] After the central part of the upper surface of the substrate W is covered by the second liquid film F2, a liquid discharge process is performed, that is, an exposure hole H is formed on the second liquid film F2 to expose the central part of the upper surface of the substrate W from the second liquid film F2, and the outer edge of the exposure hole H is extended to the periphery of the upper surface of the substrate W.

[0194] Specifically, when the blocking member 51 is in the upper position and at least one protective cover 24 is in the upper position, the upper gas valve 64 is opened and the central nozzle 55 starts to spray nitrogen (see Fig.11A The temperature of the nitrogen gas ejected from the central nozzle 55 may be room temperature or higher than room temperature. The ejection of the nitrogen gas may be started before or after the outer periphery of the second liquid film F2 extends to the outer periphery of the upper surface of the substrate W, or may be started at the same time as the outer periphery of the second liquid film F2 extends to the outer periphery of the upper surface of the substrate W. Fig.11A An example in which the nitrogen gas is started to be ejected before the outer periphery of the second liquid film F2 spreads to the outer periphery of the upper surface of the substrate W is shown.

[0195] The blocking member lifting unit 54 can place the blocking member 51 in the lower position before or after the start of nitrogen spraying, or can place the blocking member 51 in the lower position at the same time as the start of nitrogen spraying. When the central nozzle 55 sprays nitrogen, the rotary chuck 10 can rotate the substrate W at the liquid discharge speed, or can make the substrate W stand still. The liquid discharge speed is greater than the first immersion speed. The liquid discharge speed can be equal to or different from the second replacement speed. In this example, the liquid discharge speed is a speed greater than the first immersion speed and less than the rinse liquid supply speed. When the liquid discharge speed is different from the second replacement speed, the rotation speed of the substrate W can be changed before or after the start of nitrogen spraying, or can be changed at the same time as the start of nitrogen spraying.

[0196] The nitrogen gas ejected from the central nozzle 55 collides with the second liquid film F2 at the central portion of the upper surface of the substrate W, and then flows outward in all directions along the surface of the second liquid film F2. Thus, an airflow is formed that flows outward in all directions from the central portion of the upper surface of the substrate W. If the nitrogen gas is sprayed to the central portion of the second liquid film F2, the second liquid contained in the second liquid film F2 is pushed to the outside due to the pressure of the nitrogen gas. In addition, the evaporation of the second liquid is promoted by the supply of nitrogen gas. Thus, as Fig. 11B As shown in FIG. 1 , the thickness of the central portion of the second liquid film F2 is reduced, and a substantially circular exposure hole H is formed in the central portion of the second liquid film F2 (hole forming step ( Fig.10 Step S9-4)).

[0197] In addition, the force that moves the second liquid outward is applied to the second liquid on the substrate W by the nitrogen gas flowing outward along the surface of the second liquid film F2, and the second liquid flows outward along the upper surface of the substrate W. When the spin chuck 10 rotates the substrate W, centrifugal force is also applied to the second liquid on the substrate W. Fig. 11C As shown, the inner diameter and the outer diameter of the ring-shaped second liquid film F2 increase as the second liquid flows along the upper surface of the substrate W toward the outside.

[0198] When the annular first liquid film F1 remains on the outer peripheral portion of the upper surface of the substrate W, the first liquid on the outer peripheral portion of the upper surface of the substrate W is pushed outward by the second liquid and discharged from the substrate W. Thus, the first liquid film F1 is discharged from the substrate W. Thereafter, the inner periphery of the second liquid film F2 is extended to the outer periphery of the upper surface of the substrate W (hole enlarging step ( Fig.10 In step S10-4)), when the annular first liquid film F1 does not remain on the outer periphery of the upper surface of the substrate W, the inner periphery of the second liquid film F2 also extends to the outer periphery of the upper surface of the substrate W. As a result, droplets of a size that can be visually observed disappear from the upper surface of the substrate W, and the entire area of ​​the upper surface of the substrate W is exposed.

[0199] Next, the drying process is performed ( Fig.10 In step S11), the substrate W is dried by rotating the substrate W at a high speed.

[0200] Specifically, when the blocking member 51 is in the upper position, the blocking member lifting unit 54 lowers the blocking member 51 from the upper position to the lower position. In this state, the spin chuck 10 rotates the substrate W at a high rotation speed (for example, several thousand rpm) that is greater than the supply speed of the rinsing liquid. Even if droplets of a size that cannot be visually observed remain on the upper surface of the substrate W (for example, between the patterns P1), such droplets will evaporate during the period when the substrate W rotates at a high speed. Thus, the substrate W is dried. When a predetermined time has passed since the substrate W started to rotate at a high speed, the spin chuck 10 stops rotating. Thus, the rotation of the substrate W is stopped ( Fig.10 Step S12).

[0201] Next, carry out the unloading process ( Fig.10 Step S13), that is, moving the substrate W out of the chamber 4.

[0202] Specifically, the blocking member lifting unit 54 raises the blocking member 51 to the upper position, and the protective cover lifting unit 27 lowers all the protective covers 24 to the lower position. Then, the upper gas valve 64 and the lower gas valve 84 are closed, and the upper central opening 61 of the blocking member 51 and the lower central opening 81 of the rotating base 12 stop spraying nitrogen. Thereafter, the central robot CR causes the hand H1 to enter the chamber 4. After the central robot CR releases the grip of the substrate W by the plurality of chuck pins 11, the central robot CR supports the substrate W on the rotating chuck 10 with the hand H1. Thereafter, the central robot CR supports the substrate W with the hand H1 while withdrawing the hand H1 from the interior of the chamber 4. Thus, the processed substrate W is carried out of the chamber 4.

[0203] As described above, in the first to fourth embodiments, a rinsing liquid containing water is supplied to the upper surface of the substrate W held horizontally. Thereafter, the first liquid is supplied to the upper surface of the substrate W held horizontally. Thus, the rinsing liquid on the upper surface of the substrate W is replaced by the first liquid. Thereafter, the second liquid is supplied to the upper surface of the substrate W held horizontally. Thus, the first liquid on the upper surface of the substrate W is replaced by the second liquid. Therefore, the rinsing liquid is replaced by the second liquid in stages. Thereafter, the second liquid is removed from the upper surface of the substrate W, and the substrate W is dried.

[0204] The rinsing liquid on the substrate W is not directly replaced by the second liquid, but is replaced by the second liquid after being replaced by the first liquid. The solubility of the second liquid in water is lower than that of the first liquid in water. That is, the second liquid has a lower affinity for water than the first liquid. If the second liquid is supplied to the upper surface of the substrate W holding the rinsing liquid, the rinsing liquid may remain on the upper surface of the substrate W. If the amount of the rinsing liquid containing water with high surface tension remains large, when the substrate W is dried, pattern P1 (see Fig.14AIf the rinsing liquid is replaced by the first liquid having a relatively high affinity with water, the rinsing liquid remaining on the substrate W immediately before drying can be reduced.

[0205] In addition, the specific gravity of the second liquid is greater than that of the first liquid. Therefore, at the interface between the first liquid and the second liquid, the second liquid moves toward the upper surface side of the substrate W due to gravity, and the first liquid moves onto the second liquid. That is, due to the difference in specific gravity, the second liquid enters between the first liquid and the substrate W. In addition, since the surface tension of the second liquid is low and the specific gravity of the second liquid is large, the second liquid enters between the patterns P1, and the first liquid located between the patterns P1 is replaced by the second liquid. Since the second liquid with such low surface tension enters between the patterns P1, when the substrate W is dried, even if the surface of the second liquid is formed between the patterns P1, the collapse of the patterns P1 can be reduced.

[0206] The boiling point of the second liquid is above room temperature. Therefore, when the second liquid is used under room temperature, it is not necessary to cool the second liquid in order to maintain it as a liquid. In addition, the value obtained by subtracting the room temperature from the boiling point of the second liquid is below room temperature. That is, the boiling point of the second liquid is a value within the range of room temperature to twice the value of room temperature, which is relatively low relative to room temperature. If the boiling point of the second liquid is low, the speed at which the second liquid disappears from the substrate W during the drying process of the substrate W increases, so the time for the collapse force that causes the collapse of the pattern P1 to be applied to the pattern P1 can be shortened. Thus, the collapse of the pattern P1 can be reduced, and the quality of the substrate W after drying can be improved.

[0207] In the first to fourth embodiments, the first liquid on the upper surface of the substrate W is replaced with the second liquid while the substrate W is rotated at a low speed. When the supply of the second liquid is started, the upper surface of the substrate W is covered with the second liquid film F2 which is approximately circular and the first liquid film F1 which is annular and surrounds the second liquid film F2. Thereafter, the outer periphery of the second liquid film F2 slowly expands toward the outer periphery of the upper surface of the substrate W while maintaining an approximately circular state. In the case where the properties of the first liquid and the second liquid are greatly different, if the substrate W is rotated at a high speed, there is a concern that the outer periphery of the second liquid film F2 will not expand while maintaining an approximately circular state, and the first liquid will not be replaced reliably. If the substrate W is rotated at a low speed, such a phenomenon can be prevented in advance.

[0208] In the second to fourth embodiments, only a portion of the first liquid on the upper surface of the substrate W is replaced with the second liquid. As a result, the annular first liquid film F1 remains at least on the outer peripheral portion of the upper surface of the substrate W, and the second liquid is retained inside the first liquid film F1. Since the surface tension of the second liquid is low, if the entire first liquid on the upper surface of the substrate W is replaced with the second liquid, a thin second liquid film F2 is formed on the upper surface of the substrate W. In addition, since the boiling point of the second liquid is low, if the supply of new second liquid is stopped, the second liquid on the substrate W may evaporate rapidly, and a portion of the upper surface of the substrate W may be exposed from the second liquid film F2 in a short time.

[0209] In contrast, since the surface tension of the first liquid is higher than that of the second liquid, the thickness of the first liquid film F1 remaining on the outer peripheral portion of the upper surface of the substrate W is greater than the thickness of the second liquid film F2. The second liquid supplied to the upper surface of the substrate W is retained inside the annular first liquid film F1. Therefore, compared with the case where the entire first liquid on the upper surface of the substrate W is replaced with the second liquid, a thicker second liquid film F2 is formed inside the first liquid film F1. Thus, it is possible to prevent a portion of the upper surface of the substrate W from being exposed from the second liquid film F2 in a short time.

[0210] In the second to fourth embodiments, in a state where the second liquid film F2 is held on the upper surface of the substrate W, an exposure hole H is formed on the second liquid film F2 to expose only a portion of the upper surface of the substrate W. Thereafter, the outer edge of the exposure hole H is extended to the outer periphery of the upper surface of the substrate W. Thus, droplets of a size that can be visually observed disappear from the upper surface of the substrate W, and the entire area of ​​the upper surface of the substrate W is exposed. That is, the second liquid film F2 is discharged from the upper surface of the substrate W while controlling the shape of the second liquid film F2. Therefore, compared with the case where the second liquid film F2 is discharged in a disorderly manner, the quality of the substrate W after drying can be stabilized.

[0211] In the second to fourth embodiments, the inner and outer diameters of the annular second liquid film F2 having the exposure hole H formed therein and the inner diameter of the annular first liquid film F1 surrounding the second liquid film F2 are increased while the substrate W is rotated at a low speed. In the case where the properties of the first liquid and the second liquid are greatly different, if the substrate W is rotated at a high speed, there is a concern that the outer periphery of the second liquid film F2 will not extend to the outer periphery of the upper surface of the substrate W while maintaining a substantially circular shape, and the first liquid will remain on the outer periphery of the upper surface of the substrate W. If the substrate W is rotated at a low speed, such a phenomenon can be prevented in advance.

[0212] In the second to fourth embodiments, while the substrate W is rotated at a rotation speed greater than 0 and less than 50 rpm, the inner diameter and outer diameter of the annular second liquid film F2 formed with the exposure hole H and the inner diameter of the annular first liquid film F1 surrounding the second liquid film F2 are increased. Since the centrifugal force applied to the second liquid is small, the inner and outer peripheries of the second liquid film F2 are slowly expanded. Thus, the outer periphery of the second liquid film F2 can be expanded to the outer periphery of the upper surface of the substrate W while maintaining a substantially circular shape, and the amount of the first liquid remaining on the outer periphery of the upper surface of the substrate W can be reduced to zero or near zero.

[0213] In the second embodiment, warm water (pure water at a higher temperature than room temperature), which is an example of a heating fluid at a higher temperature than room temperature, is ejected toward only a portion of the lower surface of the substrate W. After the warm water collides with the lower surface of the substrate W, it spreads along the lower surface of the substrate W. The substrate W is heated by the warm water. The second liquid is heated by the substrate W. The evaporation amount of the second liquid per unit time is the largest on the side opposite to the position where the warm water collides with the lower surface of the substrate W. Therefore, the position where the exposure hole H is formed can be controlled.

[0214] In the second embodiment, when the exposure hole H is formed on the second liquid film F2 and the outer edge of the exposure hole H is extended to the outer peripheral side of the upper surface of the substrate W, warm water as an example of an anti-condensation fluid is supplied to the lower surface of the substrate W, and the temperature of the upper surface of the substrate W is maintained at a value higher than the dew point temperature of the second liquid. After the exposure hole H is formed, at least a portion of the upper surface of the substrate W is exposed, and the vapor of the second liquid floats near the upper surface of the substrate W. Therefore, by maintaining the temperature of the upper surface of the substrate W at a value higher than the dew point temperature of the second liquid, it is possible to prevent the generation of droplets of the second liquid at the exposed portion of the upper surface of the substrate W that has been exposed from the second liquid film F2. As a result, it is possible to reduce the collapse of the pattern at the exposed portion and the generation of particles.

[0215] In the third embodiment, the second liquid nozzle 43 is caused to eject the second liquid while the substrate W is rotated. In addition, the position where the second liquid ejected from the second liquid nozzle 43 collides with the upper surface of the substrate W is moved from the central portion of the upper surface of the substrate W to the outer peripheral side of the upper surface of the substrate W. After the second liquid nozzle 43 is moved, the supply of new second liquid to the central portion of the upper surface of the substrate W is stopped. In addition, the second liquid evaporates on the central portion of the upper surface of the substrate W, and moves outward from the central portion of the upper surface of the substrate W due to centrifugal force. Therefore, the exposure hole H can be formed in the central portion of the upper surface of the substrate W only by moving the second liquid nozzle 43 outward.

[0216] Next, a second embodiment will be described.

[0217] The second embodiment differs from the first embodiment mainly in that a heating plate 92 is provided instead of the lower surface nozzle 71 .

[0218] In the following Fig. 12A , Fig. 12B , Fig.13 ,and Figures 14A to 14C In Figure 1A to Figure 11C The same composition as shown is marked with Figure 1A The same reference numerals are used and their descriptions are omitted.

[0219] Fig. 12A This is a schematic diagram showing the spin chuck 10 , the blocking member 51 , and the heating plate 92 according to the second embodiment of the present invention viewed horizontally. Fig. 12B It is a schematic diagram of the spin chuck 10 and the heating plate 92 viewed from above. Fig. 12A A state in which the blocking member 51 is located in the upper position is shown.

[0220] like Fig. 12A As shown, the heating plate 92 is arranged between the substrate W and the spin base 12. The heating plate 92 includes a heating element 93 that generates Joule heat by energizing, and a housing 94 that accommodates the heating element 93. The heating element 93 and the housing 94 are arranged below the substrate W. The heating element 93 is connected to a wiring (not shown) that supplies power to the heating element 93. The temperature of the heating element 93 is changed by the control device 3. If the control device 3 causes the heating element 93 to generate heat, the entire substrate W is uniformly heated.

[0221] The housing 94 of the heating plate 92 includes a disc-shaped base portion 95 disposed below the substrate W, and a plurality of hemispherical protrusions 96 protruding upward from the upper surface of the base portion 95. The upper surface of the base portion 95 is parallel to the lower surface of the substrate W, and has an outer diameter smaller than the diameter of the substrate W. The plurality of protrusions 96 are in contact with the lower surface of the substrate W at positions away from the upper surface of the base portion 95 upward. The plurality of protrusions 96 are disposed at a plurality of positions within the upper surface of the base portion 95 so as to horizontally support the substrate W. The substrate W is horizontally supported in a state in which the lower surface of the substrate W is away from the upper surface of the base portion 95 upward.

[0222] like Fig. 12B As shown in FIG. 1 , a plurality of chuck pins 11 are arranged around the heating plate 92. The center line of the heating plate 92 is arranged on the rotation axis A1 of the substrate W. Even if the rotary chuck 10 rotates, the heating plate 92 does not rotate. The outer diameter of the heating plate 92 is smaller than the diameter of the substrate W. The difference between the outer diameter of the heating plate 92 and the diameter of the substrate W is smaller than the height of the chuck pins 11 (see FIG. 1 ). Fig. 12A . The length in the up-down direction from the upper surface 12u of the rotating base 12 to the upper end of the chuck pin 11).

[0223] like Fig. 12A As shown in FIG. 1 , the heating plate 92 is horizontally supported by a support shaft 97 extending downward from the center of the heating plate 92. The heating plate 92 can move in the up-down direction relative to the rotating base 12. The heating plate 92 is connected to a plate lifting unit 98 via the support shaft 97. The plate lifting unit 98 moves the heating plate 92 in the upper position ( Fig. 12A The position shown by the solid line in the middle) and the lower position ( Fig. 12A The upper position is a contact position where the heating plate 92 contacts the lower surface of the substrate W. The lower position is a proximity position where the heating plate 92 is disposed between the lower surface of the substrate W and the upper surface 12u of the spin base 12 in a state where the heating plate 92 is separated from the substrate W.

[0224] The plate lifting unit 98 positions the heating plate 92 at any position from the upper position to the lower position. When the heating plate 92 is raised to the upper position in a state where the substrate W is supported by the plurality of chuck pins 11 and the grip of the substrate W is released, the plurality of protrusions 96 of the heating plate 92 come into contact with the lower surface of the substrate W, and the substrate W is supported by the heating plate 92. Thereafter, the substrate W is lifted by the heating plate 92 and moves upward away from the plurality of chuck pins 11. In this state, when the heating plate 92 is lowered to the lower position, the substrate W on the heating plate 92 is placed on the plurality of chuck pins 11, and the heating plate 92 moves downward away from the substrate W. Thus, the substrate W is transferred between the plurality of chuck pins 11 and the heating plate 92.

[0225] Next, the fifth embodiment will be described.

[0226] From the loading process ( Fig.13 Step S1) to the second immersion step ( Fig.13 The process of the fifth embodiment up to step S8-2) is the same as that of the second embodiment, and therefore, the process after the liquid discharge step will be described below.

[0227] Fig.13 The following are process diagrams for explaining another example (fifth embodiment) of processing of the substrate W performed by the substrate processing apparatus 1. Figures 14A to 14C FIG. 2 is a schematic diagram showing the state of the substrate W when the fifth embodiment is performed. Fig. 12A , Fig. 12B ,and Fig.13 .for Figures 14A to 14C , with appropriate reference.

[0228] After a roughly circular second liquid film F2 covering the central portion of the upper surface of the substrate W and a ring-shaped first liquid film F1 surrounding the second liquid film F2 are formed on the upper surface of the substrate W, a liquid discharge process is performed, that is, an exposure hole H is formed on the second liquid film F2 to expose the central portion of the upper surface of the substrate W from the second liquid film F2, and the outer edge of the exposure hole H is extended to the periphery of the upper surface of the substrate W.

[0229] Specifically, when the blocking member 51 is in the upper position and at least one protective cover 24 is in the upper position, the heating plate 92 generates heat and starts heating the substrate W. The heating of the heating plate 92 may start before or after the second liquid is supplied to the substrate W, or may start at the same time as the second liquid is supplied to the substrate W. The heating plate 92 may heat the substrate W in a state of contact with the lower surface of the substrate W, or may heat the substrate W in a state of separation from the lower surface of the substrate W. The temperature of the substrate W may be changed by changing the temperature of the heating plate 92, or by changing the interval between the substrate W and the heating plate 92.

[0230] When the heating plate 92 heats the substrate W in a state of contact with the lower surface of the substrate W, the substrate W is stationary on the heating plate 92. When the heating plate 92 heats the substrate W in a state of being separated from the lower surface of the substrate W, the spin chuck 10 rotates the substrate W at a liquid discharge speed. The liquid discharge speed is greater than the first immersion speed. The liquid discharge speed may be equal to or different from the second replacement speed. In this example, the liquid discharge speed is a speed greater than the first immersion speed and less than the rinse liquid supply speed. When the liquid discharge speed is different from the second replacement speed, the rotation speed of the substrate W may be changed before or after the start of heating the substrate W, or may be changed at the same time as the start of heating the substrate W.

[0231] like Fig.14A As shown in FIG. 1 , when the heating plate 92 heats the substrate W, the first liquid and the second liquid on the upper surface of the substrate W are heated via the substrate W. This promotes the evaporation of the first liquid and the second liquid. Figure 2 ) is turned on after the heating plate 92 starts heating the substrate W. Thus, Fig. 14B As shown in FIG. 1 , the central nozzle 55 starts to eject nitrogen gas. The temperature of the nitrogen gas ejected from the central nozzle 55 may be room temperature or higher than room temperature. The nitrogen gas ejected from the central nozzle 55 collides with the second liquid film F2 at the center of the upper surface of the substrate W, and then flows outward in all directions along the surface of the second liquid film F2. Thus, a gas flow is formed that flows outward in all directions from the center of the upper surface of the substrate W.

[0232] If nitrogen gas is blown to the center of the second liquid film F2, the second liquid contained in the second liquid film F2 is pushed to the outside by the pressure of the nitrogen gas. In addition, the evaporation of the second liquid is promoted by the supply of nitrogen gas. Fig. 14B As shown in FIG. 1 , the thickness of the central portion of the second liquid film F2 is reduced, and a substantially circular exposure hole H is formed in the central portion of the second liquid film F2 (hole forming step ( Fig.13 In addition, the force for moving the second liquid outward is applied to the second liquid on the substrate W by the nitrogen gas flowing outward along the surface of the second liquid film F2, and the second liquid flows outward along the upper surface of the substrate W. When the spin chuck 10 rotates the substrate W, the centrifugal force is also applied to the second liquid on the substrate W.

[0233] The inner diameter and outer diameter of the annular second liquid film F2 increase as the second liquid flows outward along the upper surface of the substrate W. The first liquid on the outer peripheral portion of the upper surface of the substrate W is pushed outward by the second liquid and discharged from the substrate W. Fig. 14C As shown in FIG. 1 , the first liquid film F1 is discharged from the substrate W. Thereafter, the inner periphery of the second liquid film F2 is extended to the outer periphery of the upper surface of the substrate W (hole enlarging step ( Fig.13 Step S10-5)). As a result, droplets of a size that can be visually observed disappear from the upper surface of the substrate W, and the entire area of ​​the upper surface of the substrate W is exposed.

[0234] When power starts to be supplied to the heating plate 92, the entire area or almost the entire area of ​​the upper surface of the heating plate 92 generates heat. Therefore, compared with the case where a heating fluid such as warm water is sprayed toward the center of the lower surface of the substrate W, the substrate W can be heated uniformly. The temperature of the heating plate 92 when heating the substrate W may be any value as long as it is higher than room temperature. The temperature of the heating plate 92 may be higher than the boiling point of the second liquid. The value obtained by subtracting the boiling point of the second liquid from the temperature of the heating plate 92 may be lower than room temperature.

[0235] If the temperature of the upper surface of the substrate W (the surface including the pattern P1 when the pattern P1 is formed) is higher than the boiling point of the second liquid, the second liquid vaporizes at the interface between the second liquid film F2 and the substrate W, and a large number of small bubbles are interposed between the second liquid and the upper surface of the substrate W. If the second liquid vaporizes at all positions of the interface between the second liquid film F2 and the substrate W, a vapor layer including the vapor of the second liquid is formed between the second liquid film F2 and the substrate W (see Fig.14A ). As a result, the second liquid leaves the upper surface of the substrate W, and the second liquid film F2 floats out from the upper surface of the substrate W. At this time, the frictional resistance of the second liquid film F2 acting on the substrate W is so small that it can be regarded as zero. Therefore, the second liquid film F2 can be discharged from the upper surface of the substrate W with a small force.

[0236] Next, the drying process is performed ( Fig.13 In step S11), the substrate W is dried by rotating the substrate W at a high speed.

[0237] Specifically, when the heating plate 92 supports the lower surface of the substrate W, the substrate W is transferred from the heating plate 92 to a plurality of chuck pins 11, and the plurality of chuck pins 11 hold the substrate W. In addition, the blocking member lifting unit 54 lowers the blocking member 51 from the upper position to the lower position. In this state, the rotary chuck 10 rotates the substrate W at a high rotation speed (for example, several thousand rpm) that is greater than the supply speed of the rinsing liquid. Even if droplets of a size that cannot be visually observed remain on the upper surface of the substrate W (for example, between the patterns P1), such droplets will evaporate during the period when the substrate W is rotated at a high speed. Thus, the substrate W is dried. While the substrate W is rotating at a high speed, the heating plate 92 can generate heat to promote the evaporation of the droplets. When a predetermined time has passed since the substrate W started to rotate at a high speed, the rotary chuck 10 stops rotating. Thus, the rotation of the substrate W is stopped ( Fig.13 Step S12).

[0238] Next, carry out the unloading process ( Fig.13 Step S13), that is, moving the substrate W out of the chamber 4.

[0239] Specifically, the blocking member lifting unit 54 raises the blocking member 51 to the upper position, and the protective cover lifting unit 27 lowers all the protective covers 24 to the lower position. Then, the upper gas valve 64 and the lower gas valve 84 are closed, and the upper central opening 61 of the blocking member 51 and the lower central opening 81 of the rotating base 12 stop spraying nitrogen. Thereafter, the central robot CR causes the hand H1 to enter the chamber 4. After the central robot CR releases the grip of the substrate W by the plurality of chuck pins 11, the central robot CR supports the substrate W on the rotating chuck 10 with the hand H1. Thereafter, the central robot CR supports the substrate W with the hand H1 while withdrawing the hand H1 from the interior of the chamber 4. Thus, the processed substrate W is carried out of the chamber 4.

[0240] In the second embodiment, in addition to the effects of the first embodiment, the following effects can be exerted. Specifically, in the fifth embodiment, a heating plate 92 as an example of a heater arranged below the substrate W in a manner overlapping with the substrate W when viewed from above is heated. The substrate W is heated by the heating plate 92. The second liquid is heated by the substrate W. Thus, an exposure hole H penetrating the second liquid film F2 can be formed. In addition, compared with the case where a heating fluid having a higher temperature than room temperature is ejected only toward a part of the lower surface of the substrate W, the heating plate 92 can directly heat a wide range. Thus, the substrate W and the second liquid film F2 can be uniformly heated.

[0241] In the fifth embodiment, when the exposure hole H is formed on the second liquid film F2 and the outer edge of the exposure hole H is extended to the outer peripheral side of the upper surface of the substrate W, the substrate W is heated by the heating plate 92, and the temperature of the upper surface of the substrate W is maintained at a value higher than the dew point temperature of the second liquid. After the exposure hole H is formed, at least a part of the upper surface of the substrate W is exposed, and the vapor of the second liquid floats near the upper surface of the substrate W. Therefore, by maintaining the temperature of the upper surface of the substrate W at a value higher than the dew point temperature of the second liquid, it is possible to prevent the generation of droplets of the second liquid at the exposed portion of the upper surface of the substrate W that has been exposed from the second liquid film F2. As a result, it is possible to reduce the collapse of the pattern P1 at the exposed portion and the generation of particles.

[0242] Other Implementations

[0243] The present invention is not limited to the contents of the above-described embodiment, and various modifications can be made.

[0244] For example, in the first to fifth embodiments, at least one of the first and second immersion steps may be omitted.

[0245] In the first to fifth embodiments, the first liquid on the upper surface of the substrate W can be replaced with the second liquid while the substrate W is kept stationary.

[0246] In the second to fifth embodiments, the hole forming step and the hole enlarging step can be omitted. That is, after the first liquid film F1 and the second liquid film F2 are held on the upper surface of the substrate W, the drying step can be performed without forming the exposure hole H.

[0247] In the second embodiment, the exposure hole H can be formed without supplying a heating fluid such as warm water to the lower surface of the substrate W, and the outer edge of the exposure hole H can be extended to the outer periphery of the upper surface of the substrate W. If the substrate W is rotated in a state where the supply of a new second liquid to the upper surface of the substrate W is stopped, the thickness of the second liquid film F2 gradually decreases. In addition, although the second liquid flows from the inner side of the upper surface of the substrate W to a position other than the central portion of the upper surface of the substrate W, the second liquid does not flow to the central portion of the upper surface of the substrate W. Therefore, if a moment passes after the supply of the second liquid is stopped, the exposure hole H penetrating the second liquid film F2 is formed. Thus, the exposure hole H can be formed only by rotating the substrate W.

[0248] In the fourth embodiment, after the exposure hole H is formed in the second liquid film F2 by supplying nitrogen gas, the position where the nitrogen gas collides with the upper surface of the substrate W can be moved from the central portion of the upper surface of the substrate W to the outer peripheral portion of the upper surface of the substrate W. In this case, the nitrogen gas can be ejected from a scanning nozzle that can be horizontally moved in the chamber 4 instead of the central nozzle 55 disposed in the central portion of the blocking member 51.

[0249] In embodiments other than the second embodiment and the fifth embodiment, when the exposure hole H is formed in the second liquid film F2, the temperature of the upper surface of the substrate W can be maintained at a value higher than the dew point temperature of the second liquid when the outer edge of the exposure hole H is extended to the outer peripheral side of the upper surface of the substrate W. In this case, as long as the temperature of the upper surface of the substrate W is maintained at a value higher than the dew point temperature of the second liquid, a fluid at room temperature (for example, pure water at room temperature) may be supplied to the lower surface of the substrate W.

[0250] In the second embodiment, a heater other than the heating plate 92 may be arranged below the substrate W. The heater may be a lamp, or a heater other than the heating plate 92 and the lamp. The lamp may be an infrared lamp that emits infrared rays (for example, near infrared rays), or an LED lamp including a light emitting diode, or a lamp other than these.

[0251] The blocking member 51 may include a cylindrical portion extending downward from the outer circumference of the disk portion 52 in addition to the disk portion 52. In this case, when the blocking member 51 is arranged at the lower position, the substrate W held by the spin chuck 10 is surrounded by the cylindrical portion.

[0252] The blocking member 51 can rotate around the rotation axis A1 together with the spin chuck 10. For example, the blocking member 51 can be placed on the spin base 12 in a manner that does not contact the substrate W. In this case, since the blocking member 51 is connected to the spin base 12, the blocking member 51 and the spin base 12 rotate in the same direction and at the same speed.

[0253] The blocking member 51 may be omitted. However, when a liquid such as pure water is supplied to the lower surface of the substrate W, the blocking member 51 is preferably provided. This is because the blocking member 51 can be used to block droplets that go around from the lower surface of the substrate W to the upper surface of the substrate W along the outer peripheral surface of the substrate W, and droplets that bounce inward from the processing cup 21.

[0254] The substrate processing apparatus 1 is not limited to an apparatus that processes a disc-shaped substrate W, and may be an apparatus that processes a polygonal substrate W.

[0255] Two or more of all the aforementioned configurations may be combined. Two or more of all the aforementioned steps may be combined.

[0256] The plurality of chuck pins 11 are an example of a substrate holding unit. The rinse liquid nozzle 35 is an example of a rinse liquid supply unit. The first liquid nozzle 39 is an example of a first replacement unit. The second liquid nozzle 43 is an example of a second replacement unit. The rotary motor 14 is an example of a drying unit.

[0257] Although the embodiments of the present invention have been described in detail, these are merely specific examples for clarifying the technical content of the present invention, and the present invention should not be construed as being limited to these specific examples. The spirit and scope of the present invention are limited only by the appended claims.

[0258] Description of Reference Numerals

[0259] 1: Substrate processing device

[0260] 10: Rotating chuck

[0261] 11: Chuck pin

[0262] 14: Rotating motor

[0263] 35: Rinse liquid nozzle

[0264] 39: No. 1 liquid nozzle

[0265] 43: Second liquid nozzle

[0266] 55: Center nozzle

[0267] 71: Bottom surface nozzle

[0268] 73: Heating fluid valve

[0269] 75: Heater

[0270] 92: Heating plate

[0271] A1: Rotation axis

[0272] F1: 1st liquid film

[0273] F2: 2nd liquid film

[0274] H: Exposure hole

[0275] P1: Pattern

[0276] W: substrate

Claims

1. A substrate processing method, which is a method for drying the substrate while keeping the substrate horizontal, the method comprising the following steps: a rinsing liquid supplying step of supplying a rinsing liquid containing water to the upper surface of the substrate; a first replacement step of supplying a first liquid to the upper surface of the substrate, thereby replacing the rinse liquid on the upper surface of the substrate with the first liquid; a second replacement step of supplying a second liquid to the upper surface of the substrate, thereby replacing the first liquid on the upper surface of the substrate with the second liquid; and a drying step of removing the second liquid on the upper surface of the substrate to dry the substrate, The solubility of the second liquid in water is lower than the solubility of the first liquid in water, The surface tension of the second liquid is lower than the surface tension of the first liquid, The specific gravity of the second liquid is greater than the specific gravity of the first liquid, The boiling point of the second liquid is above room temperature, and a value obtained by subtracting the room temperature from the boiling point of the second liquid is below room temperature. in, The second replacement process includes the following partial replacement process: stopping the supply of the second liquid to the substrate before the entire liquid film of the first liquid disappears from the upper surface of the substrate, thereby replacing only a portion of the first liquid on the upper surface of the substrate with the second liquid, thereby maintaining the liquid film of the second liquid and the liquid film of the first liquid surrounding the liquid film of the second liquid are maintained on the upper surface of the substrate.

2. The substrate processing method according to claim 1, wherein: The rinsing liquid supplying step includes supplying the rinsing liquid to the upper surface of the substrate while rotating the substrate at a rinsing liquid supplying speed. The second replacement step includes supplying the second liquid to the upper surface of the substrate while rotating the substrate at a second replacement speed that is lower than a supply speed of the rinse liquid.

3. The substrate processing method according to claim 1, wherein: The substrate processing method further includes a liquid discharging step of discharging the liquid film of the second liquid from the upper surface of the substrate before the drying step. The liquid discharge step includes the following steps: a hole forming step of forming an exposure hole in the liquid film of the second liquid so as to expose only a part of the upper surface of the substrate; and a hole enlarging step of extending the outer edge of the exposure hole to the outer periphery of the upper surface of the substrate.

4. The substrate processing method according to claim 3, wherein: The rinsing liquid supplying step includes supplying the rinsing liquid to the upper surface of the substrate while rotating the substrate at a rinsing liquid supplying speed. The hole enlarging step includes the step of extending the outer edge of the exposure hole to the outer periphery of the upper surface of the substrate while rotating the substrate at a liquid discharge speed lower than the rinse liquid supply speed.

5. The substrate processing method according to claim 3 or 4, wherein: The hole enlarging step includes a step of extending the outer edge of the exposure hole to the outer periphery of the upper surface of the substrate while rotating the substrate at a rotation speed greater than 0 and less than 50 rpm.

6. The substrate processing method according to claim 3 or 4, wherein: The hole forming step includes a heating fluid supplying step of ejecting a heating fluid having a temperature higher than the room temperature toward only a portion of the lower surface of the substrate.

7. The substrate processing method according to claim 3 or 4, wherein: The hole forming step includes a uniform heating step of causing a heater disposed below the substrate so as to overlap the substrate in a plan view to generate heat.

8. The substrate processing method according to claim 3 or 4, wherein: The hole forming process includes the following scanning process: rotating the substrate around a vertical rotation axis passing through the center of the upper surface of the substrate, and, while spraying the second liquid toward the upper surface of the substrate, moving the position where the second liquid collides with the upper surface of the substrate from the center of the upper surface of the substrate to the peripheral side of the upper surface of the substrate.

9. The substrate processing method according to claim 3 or 4, comprising the following condensation prevention step: in parallel with the liquid discharge step, the temperature of the upper surface of the substrate is maintained at a value higher than the dew point temperature of the second liquid.

10. A substrate processing apparatus comprising: a substrate holding unit, the substrate holding unit holding the substrate horizontally; a rinsing liquid supply unit configured to supply a rinsing liquid containing water to an upper surface of the substrate held by the substrate holding unit; a first replacement unit configured to supply a first liquid to an upper surface of the substrate held by the substrate holding unit, thereby replacing the rinse liquid on the upper surface of the substrate with the first liquid; a second replacement unit that supplies a second liquid to the upper surface of the substrate held by the substrate holding unit, thereby replacing the first liquid on the upper surface of the substrate with the second liquid; and a drying unit for removing the second liquid on the upper surface of the substrate held by the substrate holding unit, thereby drying the substrate, The solubility of the second liquid in water is lower than the solubility of the first liquid in water, The surface tension of the second liquid is lower than the surface tension of the first liquid, The specific gravity of the second liquid is greater than the specific gravity of the first liquid, The boiling point of the second liquid is above room temperature, and a value obtained by subtracting the room temperature from the boiling point of the second liquid is below room temperature. in, The second replacement unit includes the following partial replacement unit: the supply of the second liquid to the substrate is stopped before the entire liquid film of the first liquid disappears from the upper surface of the substrate, thereby replacing only a portion of the first liquid on the upper surface of the substrate with the second liquid, thereby maintaining the liquid film of the second liquid and the liquid film of the first liquid surrounding the liquid film of the second liquid and being kept on the upper surface of the substrate.

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